Alkali and alkaline earth elements in follicular fluid and the likelihood of diminished ovarian reserve in reproductive-aged women: a case‒control study.

BACKGROUND: Imbalances in alkali elements (AEs) and alkaline earth elements (AEEs) cause reproductive disorders. However, it remains unclear whether AEs/AEEs in follicular fluid have a relationship with the serious reproductive disorder known as diminished ovarian reserve (DOR). METHODS: A nested case‒control study was carried out in China. Follicular fluid samples from 154 DOR patients and 154 controls were collected and assessed for nine AEs/AEE levels. Both the mixed and single effects of the elements on DOR were estimated with a Bayesian kernel machine (BKMR) and logistic regressions. RESULTS: The DOR group had higher median concentrations of Li, Na, and K in follicular fluid (all P values < 0.05). The logistic regression showed that compared with their lowest tertile, the high tertiles of K [OR:2.45 (1.67-4.43)], Li [OR: 1.89 (1.06-3.42)], and Cs [OR: 1.97 (1.10-3.54)] were significantly associated with the odds of DOR. The BKMR model reported that the DOR likelihood increased linearly across the 25th through 75th percentiles of the nine-AE/AEE mixture, while the AE group contributed more to the overall effect. CONCLUSION: This study revealed an association in which the likelihood of DOR increased with higher overall concentrations of AE/AEEs in follicular fluid. Among the nine detected elements, K, Li, and Cs exhibited significant individual associations with DOR. We provide new clues for the environmental factors on female fertility decline. TRIAL REGISTRATION: Retrospectively registered.

Influence of normal tide and the Great Tsunami as recorded through hourly-resolution micro-analysis of a mussel shell.

We report here hourly variations of Mg/Ca, Sr/Ca, and Ba/Ca ratios in a Mediterranean mussel shell (Mytilus galloprovincialis) collected at the Otsuchi bay, on the Pacific coast of northeastern Japan. This bivalve was living in the intertidal zone, where such organisms are known to form a daily or bidaily growth line comprised of abundant organic matter. Mg/Ca ratios of the inner surface of the outer shell layer, corresponding to the most recent date, show cyclic changes at 25-90 µm intervals, while no interpretable variations are observed in Sr/Ca and Ba/Ca ratios. High Mg/Ca ratios were probably established by (1) cessation of the external supply of Ca and organic layer forming when the shell is closed at low tide, and (2) the strong binding of Mg to the organic layer, but not of Sr and Ba. Immediately following the great tsunami induced by the 2011 Tohoku earthquake, Mg/Ca enrichment occurred, up to 10 times that of normal low tide, while apparent Ba/Ca enrichment was observed for only a few days following the event, therefore serving a proxy of the past tsunami. Following the tsunami, periodic peaks and troughs in Mg/Ca continued, perhaps due to a biological memory effect as an endogenous clock.

Investigation of chocolate types on the content of selected metals and non-metals determined by ICP-OES analytical technique.

Chocolate, one of the most popular sweets in the world, is consumed by people of all ages. Available data point to significant increases in consumption and production. However, successful determination of elements in chocolate is still difficult because of the characteristics of the matrix which contains a high content of organic compounds, like hydrogenated vegetable oil, vegetable fats, solids from malt extract, salts, emulsifiers, etc., causing problems with appropriate decomposition or digestion of sample. In this study, chocolate samples were prepared according to two procedures: water bath and microwave-assisted mineralisation. The use of Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) allowed us to determine the elemental composition of dark, milk, and white chocolate bars available on the Polish market as well as a cacao sample (100% cocoa powder). The elements assessed were Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, S, Sr, and Zn. The obtained results were used to compare the effectiveness of sample pre-treatment methods and to assess the correlation between the concentrations of specific elements and type of chocolate by the application of chemometric and statistical tools. The research showed that levels of analysed macro- and microelements are directly connected with the type of chocolate, characterised by the variable contents of cocoa paste and added milk. Data for all samples after mineralisation shown that among macroelements P was the most abundant, followed by Mg, Ca, Na, K, and S. The major essential element with the highest level was Fe, followed by Zn and Cu. In the group of toxic metals the highest content was obtained for Ba, then Al and Sr, but none exceeded permissible values prepared by health benefit organisations.

Element profiles in blood and teeth samples of children with congenital heart diseases in comparison with healthy ones.

BACKGROUND: Some elements were claimed to play a role in the pathogenesis of congenital heart defects (CHD) and influence the general well-being and health of these children. OBJECTIVES: We aimed to assess the levels of some elements simultaneously in the blood and teeth samples of children with cyanotic and acyanotic CHD compared with healthy children. METHODS: A total of 39 children with CHD (11 with cyanotic and 28 with acyanotic CHD) and 42 age- and sex-adjusted controls were enrolled. Levels of 13 elements, including magnesium, phosphorus, calcium, chromium, manganese, iron, copper, zinc, strontium, cadmium, lead, mercury, and molybdenum, were assessed using inductively coupled plasma mass spectrometry. RESULTS: Children with cyanotic and acyanotic CHD had significantly lower teeth calcium and calcium/phosphorus ratio as compared to the controls after adjusting for confounders. The mean blood iron level was found to be significantly higher in the cyanotic CHD group compared to the other groups. In addition, children with acyanotic CHD had significantly higher teeth copper levels, higher blood molybdenum and lower blood magnesium levels compared to the healthy control group. Blood cadmium and mercury levels were found to be significantly elevated in both the cyanotic and acyanotic CHD groups compared to the healthy control group. There were no differences in toxic metal levels of teeth in cases with CHD. CONCLUSION: Monitoring adequate and balanced gestational micronutrient intake might support not only maternal health but also fetal cardiac development and infant well-being. Supplementation of magnesium should be evaluated in patients having CHD.

Spectral analysis of Miracle Moringa tree leaves using X-ray photoelectron, laser induced breakdown and inductively coupled plasma -optical emission spectroscopic techniques.

The antioxidant Moringa oleifera (a medicinal plant) leaves (MOLs) containing diverse nutrients are highly beneficial for the human health. The MOLs upon consumption can lower the blood sugar, cure the heart diseases, and reduce the inflammation. In this perception, the "primary nutrients contents" in the dry MOLs (pellet samples) were evaluated for the first time using the XPS, LIBS and ICP-OES techniques. The XPS analysis of the MOLs showed the presence of vital elements like calcium (Ca), magnesium (Mg), manganese (Mn), copper (Cu), phosphorous (P), sulfur (S) and zinc (Zn). The LIBS analyses of the MOLs revealed the atomic and ionic spectral lines corresponding to the essential nutrients such as the Ca, Na, K, Fe, Mg, Mn, Cu, P, S and Zn. The calibration free LIBS algorithm (CF-LIBSA) was developed to quantify the content of each element in the dry MOLs. In addition, the LIBS results were validated by the analysis using ICP-OES standard analytical technique. The elemental contents in the MOLs obtained from the CF-LIBS analyses were counter verified by the ICP-OES results. Present results are highly valuable for the development of a traditional herbal medicine using the miracle MOLs.

The non-covalent complexes of α- or γ-cyclodextrin with divalent metal cations determined by mass spectrometry.

Noncovalent complexes between cyclodextrin (CD) and divalent metal cations drew growing attentions due to their applications in the pharmaceutical industry for molecular recognition. In this study, gas-phase binding of noncovalent complexes between α-, or γ-CD and divalent metal cations was investigated by electrospray ionization mass spectrometry (ESI-MS), demonstrating the formation of 1:1 stoichiometric noncovalent complexes. The binding of the complexes were furtherly confirmed by collision-induced dissociation (CID) with tandem mass spectrometry. The CID revealed the fragmentation pattern were strongly dependent on the electronic configuration of the cations and the charge separation reaction frequently took place in the cyclodextrin-complexes with transition metal cations. For the non-covalent complexes of α-CD with Mg2+, Ca2+, Sr2+ or Ba2+ at a collision energy of 25 eV, the fragments attributed to [α-CD + cation-nGlucose unit]2+ were observed (named series A). However, for the γ-CD complexes with transition metal cations Co2+, Ni2+, Cu2+ or Zn2+, apart from fragments of series A, it were observed fragment ions of [γ-CD + cation-nGlucose unit]+ (named series B), together with the Glucose unit (m/z 163.2) and its products with loss of H2O (m/z 145.2 and 126.8). The CID performed at a collision energy from 10 to 50 eV showed that the binding strength of complexes increase in the order of [α-CD + Mg]2+, [α-CD + Ca]2+, [α-CD + Sr]2+ and [α-CD + Ba]2+. Through mass spectrometric titrations, the values of dissociation constant Kd (in µmol•L-1) for the complexes of α-CD with Ca2+ or Ni2+ were obtained, which were 4.30 and 4.26, respectively.

Accumulation Pattern of Inorganic Elements in Scaly Tooth Mushroom (Sarcodon imbricatus) from Northern Poland.

Several studies have documented contamination levels and daily intake of metallic elements from foodstuffs including rice, maize, pulses, vegetables, fruits, fish, meat, egg, milk etc., however, limited literature is available on metal contamination levels in wild growing mushrooms and possible human exposure via consumption of it. Sarcodon imbricatus is an edible mushroom, commonly consumed in many parts of the world. Very few studies have been conducted on inorganic elemental composition in fruiting bodies (edible part) of this fungus. In this study, elements such as silver (Ag), aluminum (Al), barium (Ba), calcium (Ca), cadmium (Cd), cobalt (Co,) chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), phosphorous (P), lead (Pb), rubidium (Rb), strontium (Sr) and zinc (Zn) were measured in caps and stems of fruiting bodies of S. imbricatus collected from the Wdzydze forests in Central and the Augustowska Primeval forest in Eastern Poland. Results revealed that a wide variation in concentrations of various metals in caps and stems samples collected from the two forests. Toxic metallic elements such as Cd and Hg showed preferential accumulation in caps than stems samples from both the forests. However, the concentrations of Cd, Hg and Pb in the mushroom samples were below the established weekly intake tolerance limits.

Qualitative and quantitative 1 H NMR spectroscopy for determination of divalent metal cation concentration in model salt solutions, food supplements, and pharmaceutical products by using EDTA as chelating agent.

This paper introduces an 1 H NMR method to identify individual divalent metal cations Be2+ , Mg2+ , Ca2+ , Sr2+ , Zn2+ , Cd2+ , Hg2+ , Sn2+ , and Pb2+ in aqueous salt solutions through their unique signal shift and coupling after complexation with the salt of ethylenediaminetetraacetic acid (EDTA). Furthermore, quantitative determination applied for the divalent metal cations Ca2+ , Mg2+ , Hg2+ , Sn2+ , Pb2+ , and Zn2+ (limit of quantification: 5-22 µg/ml) can be achieved using an excess of EDTA with aqueous model salt solutions. An internal standard is not required because a known excess of EDTA is added and the remaining free EDTA can be used to recalculate the quantity of chelated metal cations. The utility of the method is demonstrated for the analysis of divalent cations in some food supplements and in pharmaceutical products.

Cluster and Factor Analysis of Elements in Serum and Urine of Diabetic Patients with Peripheral Neuropathy and Healthy People.

Diabetic peripheral neuropathy (DPN) is a common complication of diabetes mellitus, presented as a major teratogenic cause worldwide. This study discussed alternation and correlation of magnesium (Mg), calcium (Ca), copper (Cu), zinc (Zn), iron (Fe), chromium (Cr), and selenium (Se) among DPN patients and healthy people using multivariate statistical analysis. Fifty patients with DPN were recruited from endocrinology department, First Hospital of Jilin University between January 2010 and October 2011 and also 50 healthy subjects were enrolled at the same time. Inductively coupled plasma mass spectrometry (ICP-MS) was used to assay elements in serum and urine. Cluster analysis was used to clarify alternation of elements' homogeneity. Factor analysis was performed to evaluate the most informative kinds of elements. Mg, Ca, Zn, and Cr in DPN patients were significantly lower in serum whereas significantly higher in urine. Elements were clustered into 4 or 5 clusters based on internal association using between-groups linkage algorithm. Serum Cr, Se, and Fe were grouped, and Mg related to Ca more closely in both serum and urine in DPN. Factor analysis revealed discrepancies of elements' contribution. Cr, Se, and Fe appeared to be the most crucial factors contributing to DPN. Mg, Ca, Zn, and Cu were more influential, whereas Cr became less potent to disease. Contributed value of elements could be determined and specified using loadings in scree plot. Future studies and delicate statistical models should be applied.

Combining Multi-Element Analysis with Statistical Modeling for Tracing the Origin of Green Coffee Beans from Amhara Region, Ethiopia.

Characterization of coffee terroirs is important to determine authenticity and provide confidence for consumers to select the right product. In this regard, Amhara Region, which is located at the northwestern part of Ethiopia, produces various local coffee types with distinct cup qualities. The coffees are, however, not yet registered with certification marks or trademarks for indications of their geographical origins. This study was aimed at developing analytical methodology useful to determine the geographical origin of green coffee beans produced in Amhara Region based on multi-element analysis combined with multivariate statistical techniques. For this, a total of 120 samples of green coffee beans, collected from four major cultivating zones (West Gojjam, East Gojjam, Awi, and Bahir Dar Especial Zones) were analyzed for K, Mg, Ca, Mn, Fe, Cu, Fe, Co, Ni, Zn, Si, Cr, Cd, and Pb using inductively coupled plasma-optical emission spectroscopy. The elemental analysis data were subjected to principal component analysis (PCA) and linear discriminant analysis (LDA). PCA was used to explore the natural groupings of samples and the discriminatory ability of elements. Accordingly, the elements K, Mg, Ca, and Na were found to be the main discriminators among samples. LDA provided a model to classify the coffee samples based on their production zones with an accuracy of 94.2% and prediction ability of 93.4%. Thus, the elemental composition of green coffee beans can be used as a chemical descriptor in the authentication of coffee produced in Amhara Region.

Sensitive chemical sensor array based on nanozymes for discrimination of metal ions and teas.

Tea, originating from China, is an important part of Chinese traditional culture. There are different qualities of and producing areas for tea on the market, therefore it is necessary to discriminate between teas in a fast and accurate way. In this study, a chemical sensor array based on nanozymes was developed to discriminate between different metal ions and teas. The indicators for the sensor array are three kinds of nanozymes mimicking laccase (Cu-ATP, Cu-ADP, Cu-AMP). The as-developed sensor array successfully discriminated 12 metal ions and the detection limit was as low as 0.01 µM. The as-developed sensor array was also able to discriminate tea samples. Different kinds of tea samples appeared in different areas in the canonical score plot with different response patterns. Furthermore, in a blind experiment, we successfully discriminated 12 samples with a 100% accuracy. This sensor array integrates chemistry and food science together, realizing the simultaneous detection of several kinds of teas using a sensitive method. The as-developed sensor array would have an application in the tea market and provide a fast and easy method to discriminate between teas.

Could biological tissue preservation methods change chemical elements proportion measured by energy dispersive X-ray spectroscopy?

Energy dispersive X-ray spectroscopy (EDS) is a powerful technical tool used in the biomedical field to investigate the proportion of chemical elements of interest in research, such as heavy metal bioaccumulation and the enzymatic cofactors and nanoparticle therapy in various pathologies. However, the correct evaluation of the proportion of the elements is subject to some factors, including the method of sample preservation. In this study, we seek to investigate the effect of biological tissue preservation methods on the proportion of chemical elements obtained by the EDS methodology. For such, we used EDS to measure the proportion of chemical elements with biomedical interest in preserved livers, using three common methods for preserving biological tissues: (a) freezing, (b) paraformaldehyde fixative solution, and (c) Karnovsky solution. We found an increased level of sodium and reduced contents of potassium and copper in samples fixed in fixative solutions, when compared to frozen samples (p < 0.05). Our data indicate that preservation methods can change the proportion of chemical elements in biological samples, when measured by EDS. Frozen preservation should be preferred to retain the actual chemical content of samples and allow a correct assessment of the proportion of their elements.

Determination of inorganic cations in biological fluids using a hybrid capillary electrophoresis device coupled with contactless conductivity detection.

We describe the assembly of a hybrid electrophoresis device that contains fused silica capillaries interconnected to a microfabricated interface in a cross format for the determination of inorganic cations in biological samples. The sample transport in the proposed hybrid device was performed under gated injection mode and the separations were monitored with a capacitively coupled contactless conductivity detector. The capillary extremities were inserted into polypropylene tubes to create solution reservoirs. Sensing electrodes were produced using stainless-steel hypodermic needles previously cut with 2.0 mm length. The running composition and injection time were optimized and the best results were found using 50 mmol/L lactic acid, 20 mmol/L histidine and 3 mmol/L 18-crown-6 ether, and an electrokinetic injection time of 15 s. The separation of six inorganic cations was achieved with baseline resolution, and efficiencies were between 9.1 × 103 and 5.4 × 104 plates/m. The proposed hybrid device was explored for determining the concentration levels of inorganic cations in urine, saliva, and tear samples, employing Li+ as an internal standard. The achieved results were in good agreement with the data reported in the literature. The reliability of the proposed method ranged from 93 to 98%, thus suggesting satisfactory accuracy for bioanalytical applications.

Stability of Major Geogenic Cations in Drinking Water-An Issue of Public Health Importance: A Danish Study, 1980⁻2017.

Concentrations and spatial variations of the four cations Na, K, Mg and Ca are known to some extent for groundwater and to a lesser extent for drinking water. Using Denmark as case, the purpose of this study was to analyze the spatial and temporal variations in the major cations in drinking water. The results will contribute to a better exposure estimation in future studies of the association between cations and diseases. Spatial and temporal variations and the association with aquifer types, were analyzed with spatial scan statistics, linear regression and a multilevel mixed-effects linear regression model. About 65,000 water samples of each cation (1980⁻2017) were included in the study. Results of mean concentrations were 31.4 mg/L, 3.5 mg/L, 12.1 mg/L and 84.5 mg/L for 1980⁻2017 for Na, K, Mg and Ca, respectively. An expected west-east trend in concentrations were confirmed, mainly explained by variations in aquifer types. The trend in concentration was stable for about 31⁻45% of the public water supply areas. It is therefore recommended that the exposure estimate in future health related studies not only be based on a single mean value, but that temporal and spatial variations should also be included.

Status and interrelationship of toenail elements in Pacific children.

OBJECTIVE: Elemental deficiencies or in excess effects growth and development. Pacific population are at a disadvantage due to food insecurity as compared to New Zealand European households. This study aims to evaluate the status and interrelationship of elements (essential, non-essential and toxic) in nine-year-old Pacific children who were part of the Pacific Island Families Study living in New Zealand. MATERIALS AND METHODS: This observational study included 278 eligible nine-year-old children. Essential elements (including calcium, chromium, cobalt, copper, iodine, iron, magnesium, manganese, selenium, zinc, molybdenum), non-essential and toxic elements (arsenic, aluminum, antimony, boron, cadmium, lead, mercury, nickel,) were determined in toenails and after acid digestion, analysed using inductively coupled plasma mass spectrometry. Principal component analysis and multivariate analysis of covariance was used to identify differences in the groups of elements and the inter-correlations between elements. RESULTS: The mean calcium (868µg/g Ca), selenium (0.35µg/g Se) and zinc (129µg/g Zn) concentrations were lower while the mean cadmium (0.21µg/g Cd) lead (0.86µg/g Pb) and mercury (0.72µg/g Hg) concentrations were higher than the optimal health requirements. Ethnic differences in relation to toenail elemental concentrations were observed for aluminium and iron. Gender differences were observed for aluminium, antimony, arsenic and lead. Selenium and molybdenum were inversely associated with mercury. Manganese, zinc and calcium were positively associated. CONCLUSIONS: This research contributes to the understanding of the elemental concentrations for Pacific children by using tissue samples from toenails, which improves the completeness of sampling than other tissues and provides a longer exposure time frame. The study also reports several inter-correlations between essential, non-essential and toxic elements in Pacific Island population.

Simultaneous Determination of Arsenic, Cadmium, Calcium, Chromium, Cobalt, Copper, Iron, Lead, Magnesium, Manganese, Molybdenum, Nickel, Selenium, and Zinc in Fertilizers by Microwave Acid Digestion and Argon Inductively Coupled Plasma-Optical Emission Spectrometry Detection: Single-Laboratory Validation, First Action 2017.02.

A single-laboratory validation method for the simultaneous determination of nutrient and non-nutrient metals in commercial fertilizers was reviewed by the AOAC Expert Review Panel (ERP) and Stakeholder Panel for Fertilizers at the 2017 midyear AOAC INTERNATIONAL meeting. In addition to using 15 of the original 30 fertilizer materials from the previous Method 2006.03 collaborative study, NIST Standard Certified Reference Material 695 and Magruder check sample 2009-06 were also incorporated as accuracy, recovery, and repeatability materials. Method 2017.02 is suitable for the simultaneous determination of arsenic, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel, selenium, and zinc in all major types of commercial fertilizer products by microwave digestion and inductively coupled plasma-optical emission spectroscopy analysis. With recoveries ranging from 92.8 to 103.2% for analytes above the LOQs, improved RSDs, and enhanced efficiency as compared with the previous method, Method 2006.03, the ERP recommended this method for First Action Official MethodsSM Status.

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique.

A novel electrochemical cell based on a CaF2 solid-state electrolyte has been developed to measure the electromotive force (emf) of binary alkaline earth-liquid metal alloys as functions of both composition and temperature in order to acquire thermodynamic data. The cell consists of a chemically stable solid-state CaF2-AF2 electrolyte (where A is the alkaline-earth element such as Ca, Sr, or Ba), with binary A-B alloy (where B is the liquid metal such as Bi or Sb) working electrodes, and a pure A metal reference electrode. Emf data are collected over a temperature range of 723 K to 1,123 K in 25 K increments for multiple alloy compositions per experiment and the results are analyzed to yield activity values, phase transition temperatures, and partial molar entropies/enthalpies for each composition.

Alkaline-earth elements of scalp hair and presence of hypertension in housewives: A perspective of chronic effect.

The relationship between population intakes of alkaline-earth elements (AEEs) and hypertension risk remains under discussion. Hair AEE concentrations can indicate their intake levels into human body. Thus, we aimed to investigate an association of hair AEE concentrations with hypertension risk, and the potential effect of dietary habit on this association. We recruited 398 housewives [163 subjects with hypertension (case group) and 235 subjects without hypertension (control group)] in Shanxi Province of north China. The scalp hair grown in the recent 2 years of each subject was collected and analyzed for the four concerned AEEs [i.e. calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba)]. Our study results revealed that median concentrations (µg/g hair) of hair AEEs in the case group were systematically lower than those in control group [i.e. 701 vs. 1271 of Ca, 55.2 vs. 88.3 of Mg, 4.60 vs. 10.4 of Sr, and 1.02 vs. 1.68 of Ba]. Lower levels of the four individual AEEs of hair were associated with an increased presence of hypertension, respectively. Moreover, hair AEE concentrations were all positively correlated with the ingestion frequencies of meat, eggs, fresh vegetables, and fruits, while negatively with that of salted vegetables. A high ingestion frequency of fresh vegetables was associated with a lower prevalence of hypertension with or without adjusting confounders, while salted vegetables revealed a reverse tend. It was concluded that low hair AEEs, as markers of their long-term dietary intake, were associated with the presence of hypertension in a rural Chinese women.

Characterization of Final Action Official MethodSM 2011.19 and First Action Official Method 2015.06 Performance at Analyte Levels Corresponding to CODEX STAN 72 (1981) Minimum Levels.

A limited single-laboratory validation (SLV) was conducted in the authors' laboratory to investigate the performance of AOAC Official MethodsSM 2011.19 Determination of Chromium (Cr), Selenium (Se), and Molybdenum (Mo) in Infant Formula and Adult Nutritional Products by Inductively Coupled Plasma/Mass Spectrometry and 2015.06 Determination of Minerals and Trace Elements in Infant Formula and Adult/Pediatric Nutritional Formula by Inductively Coupled Plasma/Mass Spectrometry at analyte levels below the practical LOQs (PLOQs) already published for these Final Action Official Methods. This work was needed to verify that the actual LOQs were below the minimum requirements for minerals in infant formula as given in CODEX STAN 72 (1981). Linearity studies at low levels were conducted as well as the analysis of blanks over multiple days to establish the LOQs (as opposed to PLOQs) for these nutrients. Several placebo matrixes from the AOAC Stakeholder Panel on Infant Formula and Adult Nutritionals (SPIFAN) program were tested over multiple days at two different sample sizes to quantitate the effect of doubling the sample size given in the original publications. The SLV results indicate that both methods can meet the Codex minimum requirements as-is, without modification of the methods, albeit with a relaxation of the stringent precision criteria originally established for these methods by SPIFAN. Precision can be improved by doubling the sample size, but this step is not necessary to use the method for its intended purpose. A concurrent collaborative study of Method 2015.06 showed that the RSDR obtained across eight laboratories for several infant formula placebos containing mineral concentrations between the PLOQ and LOQ were indeed worse than SPIFAN expectations, but reasonable Horwitz ratios (HorRat) were nonetheless obtained for these analytes.

Prediction of alkaline earth elements in bone remains by near infrared spectroscopy.

An innovative methodological approach has been developed for the prediction of the mineral element composition of bone remains. It is based on the use of Fourier Transform Near Infrared (FT-NIR) diffuse reflectance measurements. The method permits a fast, cheap and green analytical way, to understand post-mortem degradation of bones caused by the environment conditions on different skeletal parts and to select the best preserved bone samples. Samples, from the Late Roman Necropolis of Virgen de la Misericordia street and En Gil street located in Valencia (Spain), were employed to test the proposed approach being determined calcium, magnesium and strontium in bone remains and sediments. Coefficients of determination obtained between predicted values and reference ones for Ca, Mg and Sr were 90.4, 97.3 and 97.4, with residual predictive deviation of 3.2, 5.3 and 2.3, respectively, and relative root mean square error of prediction between 10% and 37%. Results obtained evidenced that NIR spectra combined with statistical analysis can help to predict bone mineral profiles suitable to evaluate bone diagenesis.