Evaluation of potential human health risks associated with Li and their relationship with Na, K, Mg, and Ca in Romania's nationwide drinking water.

Background: Increasing lithium (Li) demand worldwide due to its properties and role in renewable energy will raise water reservoir pollution and side effects on human health. Divergent results regarding Li concentration in water and affective disorders are found in the literature, which is why regional reports are expected. Objective: The present study evaluated the occurrence and human health risks resulting from oral exposure, respectively, and the relationship between alkali metals (Li, Na, and K) and minerals (Mg, Ca) in balanced purified water (bottled) and spring water. Methods: The ICP-MS technique was used to measure a national database with 53 bottled and 42 spring water samples randomly selected. One-way ANOVA, Pearson correlation, and HCA analysis were applied to assess the possible relationship between metals in water. The possible side effects of Li poisoning of water resources on human health have been evaluated using the Estimated Daily Intake Index (EDI) and Total Hazard Quotient (THQ). Results: The toxic metals (As, Hg, and Pb) were measured, and the results indicate values above the detection limit of 22.3% of samples in the case of lead but not exceeding the safety limits. Depending on the water sources, such as bottled and spring water, the Li concentration varied between 0.06-1,557 and 0.09-984% µg/L. We found a strong positive correlation between Li and Na and Mg, varying between bottled and spring waters (p% <%0.001). Li exceeded the limit set by the Health-Based Screening Level (HBSL) in 41.37 and 19% of bottled and spring water samples. The oral reference doses (p-RfDs) for the noncancer assessment of daily oral exposure effects for a human lifetime exceeded threshold values. The THQ index shows potential adverse health effects, requiring further investigations and remedial actions in 27.58% of approved bottled waters and 2.38% of spring waters. Conclusion: We can conclude that water is safe based on the Li concentration found in drinking water and supported by a gap in strict regulations regarding human Li ingestion. The present study can serve decision-makers and represent a starting database with metals of interest for further clinical studies. Decision-makers can also use it to find solutions for sustainable management of clean and safe drinking water.

Lithium Content and Its Nutritional Beneficence, Dietary Intake, and Impact on Human Health in Edibles from the Romanian Market.

Lithium (Li) is present in human nutrition based on food intake, and several studies recommend it for treating mood disorders, even if the biological proprieties and biochemical mechanisms represent the basis for its use as an essential element. The Li content was evaluated using the inductively coupled plasma mass spectrometry technique (ICP-MS) in 1071 food and beverage samples from the Romanian market. The results show that Li had a decreasing mean concentration in the food samples as follows: vegetables leafy > bulbous > fructose > leguminous > egg whites > root vegetables > milk products > egg yolks > meats. Approximately a quarter of all data from each dataset category was extreme values (range between the third quartile and maximum value), with only 10% below the detection limit. Mean Li concentration indicated higher values in red wine, white wines, beers, and fruit juice and lower in ciders and bottled waters. A particular interest was addressed to plants for teas and coffee seeds, which showed narrow amounts of Li. For both food and beverages, two similar matrices, including egg whites and yolks and white and red wines, were found to have significant differences, which explains the high variability of Li uptake in various matrices. For 99.65% of the analyzed samples, the estimated daily intake of Li was below the provisional subchronic and chronic reference dose (2 µg/kgbw/day) for adverse effects in several organs and systems. Even so, a risk occurs in consuming bulbous vegetables (Li > 13.47 mg/kg) and fructose solano vegetables (Li > 11.33 mg/kg). The present study's findings indicate that ingesting most of the analyzed beverages and food samples could be considered safe, even if future studies regarding Li content, nutritional aspects, and human cohort diseases must be conducted.

Elemental Profile in Chicken Egg Components and Associated Human Health Risk Assessment.

Egg is a food product of high nutritional quality, extensively consumed worldwide. The objectives of this study were the determination of the elemental profile in eggs (egg white, yolk, and eggshell), the estimation of the non-carcinogenic health risk associated with the presence of heavy metals in investigated egg samples, and the development of statistical models to identify the best predictors for the differentiation of egg components. The assessments were carried out in a total set of 210 samples, comprising home-produced and commercial eggs, using inductively coupled plasma mass spectrometry. The results suggested measurable differences amongst hen eggs coming from different husbandry systems. The statistical models employed in this study identified several elemental markers that can be used for discriminating between market and local producer samples. The non-carcinogenic risk related to the consumption of the analyzed egg samples was generally in the safe range for the consumers, below the maximum permitted levels set by Romanian and European legislation. Food contamination is a public health problem worldwide, and the risk associated with exposure to trace metals from food products has aroused widespread concern in human health, so assessing the heavy metal content in food products is mandatory to evaluate the health risk.

Comparative Amino Acid Profile and Antioxidant Activity in Sixteen Plant Extracts from Transylvania, Romania.

In addition to the naturopathic medicines based on the antiseptic, anti-inflammatory, anticancer, or antioxidant properties of plant extracts that have been capitalized upon through the pharmaceutical industry, the increasing interest of the food industry in this area requires potent new materials capable of supporting this market. This study aimed to evaluate the in vitro amino acid contents and antioxidant activities of ethanolic extracts from sixteen plants. Our results show high accumulated amino acid contents, mainly of proline, glutamic, and aspartic acid. The most consistent values of essential amino acids were isolated from T. officinale, U. dioica, C. majus, A. annua, and M. spicata. The results of the 2,2-diphenyl-1-pycrylhydrazyl (DPPH) radical scavenging assay indicate that R. officinalis was the most potent antioxidant, followed by four other extracts (in decreasing order): T. serpyllum, C. monogyna, S. officinalis, and M. koenigii. The network and principal component analyses found four natural groupings between samples based on DPPH free radical scavenging activity content. Each plant extracts' antioxidant action was discussed based on similar results found in the literature, and a lower capacity was observed for most species. An overall ranking of the analyzed plant species can be accomplished due to the range of experimental methods. The literature review revealed that these natural antioxidants represent the best side-effect-free alternatives to synthetic additives, especially in the food processing industry.

New Trends in Separation Techniques of Lithium Isotopes: A Review of Chemical Separation Methods.

In terms of isotopic technologies, it is essential to be able to produce materials with an enriched isotopic abundance (i.e., a compound isotopic labelled with 2H, 13C, 6Li, 18O or 37Cl), which is one that differs from natural abundance. The isotopic-labelled compounds can be used to study different natural processes (like compounds labelled with 2H, 13C, or 18O), or they can be used to produce other isotopes as in the case of 6Li, which can be used to produce 3H, or to produce LiH that acts like a protection shield against fast neutrons. At the same time, 7Li isotope can be used as a pH controller in nuclear reactors. The COLEX process, which is currently the only technology available to produce 6Li at industrial scale, has environmental drawbacks due to generation of Hg waste and vapours. Therefore, there is a need for new eco-friendly technologies for separation of 6Li. The separation factor of 6Li/7Li with chemical extraction methods in two liquid phases using crown ethers is comparable to that of COLEX method, but has the disadvantages of low distribution coefficient of Li and the loss of crown ethers during the extraction. Electrochemical separation of lithium isotopes through the difference in migration rates between 6Li and 7Li is one of the green and promising alternatives for the separation of lithium isotopes, but this methodology requires complicated experimental setup and optimisation. Displacement chromatography methods like ion exchange in different experimental configurations have been also applied to enrich 6Li with promising results. Besides separation methods, there is also a need for development of new analysis methods (ICP-MS, MC-ICP-MS, TIMS) for reliable determination of Li isotope ratios upon enrichment. Considering all the above-mentioned facts, this paper will try to emphasize the current trends in separation techniques of lithium isotopes by exposing all the chemical separation and spectrometric analysis methods, and highlighting their advantages and disadvantages.

Evaluating the Chemical Hazards in Wine Production Associated with Climate Change.

The climate warming trend challenges the chemical risk associated with wine production worldwide. The present study investigated the possible difference between chemical wine profile during the drought year 2012 compared to the post-drought year 2013. Toxic metals (Cd and Pb), microelements (Mn, Ni, Zn, Al, Ba, and Cu), macroelements (Na, Mg, K, Ca, and P), isotopic ratios (87Sr/86Sr and 206Pb/207Pb), stable isotopes (δ18O, δ13C, (D/H)I, and (D/H)II), and climatic data were analyzed. The multivariate technique, correlation analysis, factor analysis, partial least squares-discriminant analysis, and hierarchical cluster analysis were used for data interpretation. The maximum temperature had a maximum difference when comparing data year apart. Indeed, extreme droughts were noted in only the spring and early summer of 2012 and in 2013, which increased the mean value of ground frost days. The microelements, macroelements, and Pb presented extreme effects in 2012, emphasizing more variability in terms of the type of wine. Extremely high Cd values were found in the wine samples analyzed, at up to 10.1 µg/L. The relationship between precipitation and δ18O from wine was complex, indicating grape formation under the systematic influence of the current year precipitation, and differences between years were noted. δ13C had disentangled values, with no differentiation between years, and when coupled with the deuterium-hydrogen ratio, it could sustain the hypothesis of possible adulteration. In the current analysis, the 87Sr/86Sr showed higher values than in other Romanian studies. The temperature had a strong positive correlation with Pb, while the ground frost day frequency correlated with both Pb and Cd toxic elements in the wine. Other significant relationships were disclosed between the chemical properties of wine and climate data. The multivariate statistical analysis indicated that heat stress had significant importance in the chemical profile of the wine, and the ground frost exceeded the influence of water stress, especially in Transylvania.

Assessing the Health Risk and the Metal Content of Thirty-Four Plant Essential Oils Using the ICP-MS Technique.

Natural ecosystems are polluted with various contaminants, and among these heavy metals raise concerns due to their side effects on both environment and human health. An investigation was conducted on essential oil samples, comparing similar products between seven producers, and the results indicated a wide variation of metal content. The recommended limits imposed by European Union regulations for medicinal plants are exceeded only in Mentha × pipperita (Adams, 0.61 mg/kg). Except for Thymus vulgaris, the multivariate analysis showed a strong correlation between toxic and microelements (p < 0.001). We verified plant species−specific bioaccumulation patterns with non-metric multidimensional scaling analysis. The model showed that Adams, Doterra, Hypericum, and Steaua Divina essential oils originated from plants containing high micro and macroelement (Cu, Mn, Mg, Na) levels. We noted that the cancer risk values for Ni were the highest (2.02 × 10−9−7.89 × 10−7). Based on the target hazard quotient, three groups of elements were associated with a possible risk to human health, including As, Hg, and Cd in the first group, Cr, Mn, Ni, and Co in the second, and Zn and Al in the third. Additionally, the challenge of coupling inter-element relationships through a network plot analysis shows a considerable probability of associating toxic metals with micronutrients, which can address cumulative risks for human consumers.

Accumulation and ecotoxicological risk assessment of heavy metals in surface sediments of the Olt River, Romania.

Heavy metal pollution of river freshwater environments currently raises significant concerns due to the toxic effects and the fact that heavy metal behavior is not fully understood. This study assessed the contamination level of eight heavy metals and trace elements (Cr, Ni, Cu, Zn, As, Pb, Cd, and Hg) in the surface sediments of 19 sites in 2018 during four periods (March, May, June, and October) in Olt River sediments. Multivariate statistical techniques were used, namely, one-way ANOVA, person product-moment correlation analysis, principal component analysis, hierarchical cluster analysis, and sediment quality indicators such as the contamination factor and pollution load index. The results demonstrated higher contents of Ni, Cu, Zn, As, Pb, Cd, and Hg, with values that were over 2.46, 4.40, 1.15, 8.28, 1.10, 1.53, and 3.71 times more, respectively, compared with the national quality standards for sediments. We observed a positive significant statistical correlation (p < 0.001) in March between elevation and Pb, Ni, Cu, Cr, and Zn and a negative correlation between Pb and elevation (p = 0.08). Intermetal associations were observed only in March, indicating a relationship with river discharge from spring. The PCA sustained mainly anthropogenic sources of heavy metals, which were also identified through correlation and cluster analyses. We noted significant differences between the Cr and Pb population means and variances (p < 0.001) for the data measured in March, May, June, and October. The contamination factor indicated that the pollution level of heavy metals was high and significant for As at 15 of the 19 sites. The pollution load index showed that over 89% of the sites were polluted by metals to various degrees during the four periods investigated. Our results improve the knowledge of anthropogenic versus natural origins of heavy metals in river surface sediments, which is extremely important in assessing environmental and human health risks and beneficial for decision-maker outcomes for national freshwater management plans.

ICP-MS Assessment of Essential and Toxic Trace Elements in Foodstuffs with Different Geographic Origins Available in Romanian Supermarkets.

The present study was conducted to quantify the daily intake and target hazard quotient of four essential elements, namely, chromium, cobalt, nickel, and copper, and four toxic trace elements, mercury, cadmium, lead, and arsenic. Thirty food items were assigned to five food categories (seeds, leaves, powders, beans, and fruits) and analyzed using inductively coupled plasma-mass spectrometry. Factor analysis after principal component extraction revealed common metal patterns in all foodstuffs, and using hierarchical cluster analysis, an association map was created to illustrate their similarity. The results indicate that the internationally recommended dietary allowance was exceeded for Cu and Cr in 27 and 29 foodstuffs, respectively. According to the tolerable upper level for Ni and Cu, everyday consumption of these elements through repeated consumption of seeds (fennel, opium poppy, and cannabis) and fruits (almond) can have adverse health effects. Moreover, a robust correlation between Cu and As (p < 0.001) was established when all samples were analyzed. Principal component analysis (PCA) demonstrated an association between Pb, As, Co, and Ni in one group and Cr, Cu, Hg, and Cd in a second group, comprising 56.85% of the total variance. For all elements investigated, the cancer risk index was within safe limits, highlighting that lifetime consumption does not increase the risk of carcinogens.

Past and present anthropic environmental stress reflect high susceptibility of natural freshwater ecosystems in Romania.

The concentrations of twelve heavy metals and trace elements (Cr, Mn, Co, Ni, Cu, As, Cd, Pb, Hg, Zn, Fe, and Al) in bed sediment and river freshwater that received sewage discharge, industrial wastewater inputs and mining residue were discussed. Spatial distribution, intra-annual trends and diffuse flux in 2019 in the middle and lower reaches of Olt River Basin (ORB) were investigated using inductively coupled mass spectrometry (ICP-MS) and atomic absorption spectroscopy (AAS). We applied correlation and principal component analysis (PCA) to quantify metal distribution relationship within environmental factors (pH, air temperature) and organic matter existing in the ORB. Moreover, the 87Sr/86Sr and 206Pb/207Pb isotope ratios analysis was employed to conclude the possible origin of the contamination. PCA analysis categorized metal presence in the four-component model, which explains 91% (May), 92% (July) and 93% (September) of the variance and indicates the potential origins of pollutants. The HCA and correlation analysis emphasized the relationship between trace elements, heavy metals in water and sediments and physicochemical characteristics of water. It was observed a high discrepancy in metal distribution between riverbed sediments and water body. In September, correlation indices highlighted sparse positive relationship with trace elements in water and mainly negative correlation values with trace elements from sediments. The origin of pollutants in sediments and water appear to be both natural and human-related activities. In all seasons increased the total exchangeable concentration of Ni, Cu and Zn in the sediments downstream sewage treatment plants and upstream of dams. The consideration of environmental factors and physicochemical characteristics of water is required to develop strategies for pollution management, assessment and mitigation in the actual condition of climate change. This study evaluated the heavy metals pollution in the Olt River Basin over three periods in 2019 under human-induced changes.

Quantification of selected antidepressants and antipsychotics in clinical samples using chromatographic methods combined with mass spectrometry: A review (2006-2015).

BACKGROUND: Psychiatric disorders contribute significantly to worldwide morbidity and mortality. In the case of depression and schizophrenia, effective drug therapy is available but 30-50% of patients do not respond sufficiently to the initial treatment regimen. Apart from the development of new molecules, it is desirable to optimize treatment outcomes with agents that are currently available. Therapeutic drug monitoring (TDM) is a suitable and widely accepted approach for improving the efficacy and safety of these drugs. METHODS: A review of the relevant literature published between 2006 and January 2015. RESULTS AND CONCLUSIONS: This review describes major advances and drawbacks in the field of chromatography coupled with single or tandem mass spectrometry (LC-MS, LC-MS/MS and GC/MS) of selected antidepressants (agomelatine, vilazodone) and antipsychotics (iloperidone, asenapine, amisulpride, aripiprazole, melperone, zotepine, ziprasidone). The high specificity in combination with high sensitivity makes these techniques an attractive complementary method to traditional procedures used in routine practice for TDM.

Arrival time distributions of product ions reveal isomeric ratio of deprotonated molecules in ion mobility-mass spectrometry of hyaluronan-derived oligosaccharides.

Hyaluronic acid is a naturally occurring linear polysaccharide with substantial medical potential. In this work, discrimination of tyramine-based hyaluronan derivatives was accessed by ion mobility-mass spectrometry of deprotonated molecules and nuclear magnetic resonance spectroscopy. As the product ion mass spectra did not allow for direct isomer discrimination in mixture, the reductive labeling of oligosaccharides as well as stable isotope labeling was performed. The ion mobility separation of parent ions together with the characteristic fragmentation for reduced isomers providing unique product ions allowed us to identify isomers present in a mixture and determine their mutual isomeric ratio. The determination used simple recalculation of arrival time distribution areas of unique ions to areas of deprotonated molecules. Mass spectrometry data were confirmed by nuclear magnetic resonance spectroscopy.