Profile of inorganic elements of seaweed from the Brazilian Northeast coast.

The contents of 24 elements were determined in seven species of macroalgae collected in Ceara-Brazil, in the rainy and dry seasons of 2022. The samples were digested, and the analytes were quantified by ICP-OES and Hg by direct analyzer. The CRM CD-200 was analyzed for accuracy and obtained recoveries were higher than 95 %. The seaweed species have different inorganic element profiles with predominant elements being: Ca, K, Na, Mg and P. The Sargassum vulgare species stood out for its Hg and As contents (1.479 ± 0.005 mg kg-1 and 172 ± 6 mg kg-1, both in the rainy seasons). Ulva lactuca attracted attention for its high concentration of V (46.4 ± 3.4 mg kg-1, rainy season). In general, the elemental content levels in the macroalgae samples were higher in the rainy season. Long-term studies to comprehend the effect of seasonality on the elemental composition of seaweed must be carried out.

Magnetic solid phase extraction as a nonchromatographic method for the quantification of ultratrace inorganic arsenic in rice by inductively coupled plasma-optical emission spectrometry (ICP OES).

An alternative analytical method was developed for the quantification of inorganic arsenic (iAs) in rice by ICP OES. Iron nanoparticles modified with an organophosphorus compound were used as the solid phase for MSPE of iAs from the plant matrix. The MSPE procedure was performed using 4 mL of a buffer solution with pH 4.0, 20 mg of the nanomaterial, and a 15-min extraction time. The total As (tAs) by ICP OES was also quantified using the same MSPE procedure after solubilization of the samples by a block digester. The accuracy of tAs and iAs quantification was verified using CRM NIST 1568b (97 % and 101 % recovery, respectively). The precision (RSD < 15 %) and LOD and LOQ (1.08 and 3.70 µg kg-1, respectively) of the proposed method were satisfactory. The rice samples had tAs contents between 0.090 and 0.295 mg kg-1 and iAs mass fractions between 0.055 and 0.109 mg kg-1.

Wild shrimp have an order of magnitude higher arsenic concentrations than farmed shrimp from Brazil illustrating the need for a regulation based on inorganic arsenic.

BACKGROUND: Shrimp is a worldwide food commodity, it is a source of several nutrients and vitamins; however, this food is one of the major sources of arsenic for humans. Legislation around the world set limits for the concentration of this element in crustaceans but is mainly concerned with total analysis. Although, arsenic species have different toxicities and total analysis could be ineffective for making decisions about food security. METHODS: Samples of wild (Farfantepenaeus brasiliensis) and farmed shrimps (Litopenaeus vannamei) from NE Brazil were fractionated in subsamples of carapace, muscle tissue and viscera. The whole shrimp as well as the animal tissue fractions were decomposed using microwave digestion and total arsenic was analyzed by mass spectrometry inductively coupled plasm (ICP-MS). The water-soluble arsenic species were extracted, and the extract was carried for speciation analysis using HPLC-ICP-MS with an anionic and cationic column. RESULTS: Total As in wild shrimp samples exceeded Brazilian and USA food legislation by one order of magnitude, with concentrations of 11.5 ± 0.5 mg kg-1, while farmed shrimp had significantly lower total arsenic levels (0.53 ± 0.09 mg kg-1). More than 60% of the As was in the edible fraction in the wild shrimp, while in farmed shrimp this was less than 50%. The speciation analysis showed that arsenobetaine (AsB) was the predominant As form and iAs was below the Chinese legislation levels (iAs <0.50 mg kg-1) for shrimp in both species. CONCLUSION: The arsenic uptake in wild and farmed shrimp was discussed and some differences were found related to feed and salinity. About legislation, it has been concluded that most food legislations that consider only tAs are not appropriate to assess the toxicity of As in seafood. It is necessary to update the legislation of food control agencies to insert As speciation analysis in their protocols.

Non-chromatographic arsenic speciation analyses in wild shrimp (Farfantepenaeus brasiliensis) using functionalized magnetic iron-nanoparticles.

A new iron-magnetic nanomaterial functionalized with organophosphorus compound was used as solid-phase for arsenic speciation analysis in seafood samples by ICP-MS. The procedure was optimized using chemometric tools and the variables pH = 4.0, 15 min extraction time, and 20 mg of mass of material were obtained as the optimum point. The inorganic arsenic (iAs) extracted using nanoparticles presented concentrations between 20 and 100 µg kg-1 in the evaluated samples. The method was validated for accuracy using CRMs DOLT-5 and DORM-4. It was possible to reuse the same magnetic nanomaterial for 6 successive cycles, and we obtained a detection limit of 16.4 ng kg-1. The proposed method is suitable for the use of inorganic speciation of As, presenting good accuracy, precision, relatively low cost, and acquittance to green chemistry principles.

The concentration of polyphenolic compounds and trace elements in the Coffea arabica leaves: Potential chemometric pattern recognition of coffee leaf rust resistance.

Coffee (Coffea arabica L.) is an important commodity, involving about 500 million people from the cultivation of the coffee trees to final consumption of infusions of the ground roasted coffee beans. In contrast to a considerable amount of research performed on green coffee beans, there are relatively few studies regarding the chemical constituents of coffee leaves. Hemileia vastatrix is a parasite, specific to coffee plants and causes coffee leaf rust, which is a very destructive disease. Some coffee plants have natural resistance which is mainly linked to a gene and specific host resistance response. An increase in flavonoid production may be related to fungal disease resistance, with the levels and flavonoid types being an early physiological response to rust infection. Trace inorganic elements can be related to many roles in the defense response of higher plants and can be used as a biomarker for some diseases. To address this, coffee leaves from 16 different cultivars of Coffea arabica were harvested from Minas Gerais, Brazil (susceptible and resistant to rust) and their polyphenolic compounds were extracted using the QuEChERS technique and quantitated by HPLC-ESI-MS. The same leaves were decomposed using an acid mixture in a block digester and the content of Al, Cu, Mg, Mn, Ni, Sn and Zn was quantitated by ICP-OES. Principal component analysis (PCA) was applied and we could establish a relation between polyphenolic and trace element concentration in the leaves with resistance to rust infection. On this basis in this preliminary study we were able to separate the resistant from the susceptible cultivars. The main compounds responsible for this differentiation were the content of chlorogenic acid and magnesium in the leaves. The content of polyphenolic compounds was lower in susceptible cultivars and a diametric effect was observed between Mn and Mg concentrations. This study shows potential for the discrimination of resistant and susceptible coffee trees based on the analyses of both trace element and polyphenolic concentration.

Inorganic content of rock dust waste from northwest of Rio de Janeiro, Brazil: do environmental risks incur from its use as natural fertilizer?

The ornamental rock exploration and coating industry has led to significant environmental impacts due to the inadequate manner in which these residues are released into the environment. This impact may be reduced by using these residues for soil enrichment, as they contain high levels of inorganic nutrients. However, some elements may be potential contaminants, thus requiring a thorough previous research before employing these substances in agriculture. In this context, this study aims to determine potentially toxic elements present in rock dust residues, As, Cd, Cr, Cu, Pb, and V, through Inductively Coupled Plasma Optical Emission Spectroscopy (ICP OES) after wet decomposition. Cd concentrations in residual rock dust waste surpassed the maximum limit established by the Brazilian Ministry of Agriculture, Livestock and Supply stipulated in normative instruction No. 5/2016 for remineralizers and substrates for plants intended for agriculture. In addition, the official digestion method adopted by the Brazilian Agricultural Research Corporation Embrapa (used for soil analysis) was used for a rock dust waste analysis and compared to two different block digester-based procedures. Accuracy was confirmed by using the Certified Reference Material (CRM) NIST SRM 1646a (Estuarine Sediments) and addition/recovery tests. The limits of detection for the aforementioned elements, after aqua-regia-induced digestion, were of 0.07 mg kg-1 for As, 0.06 mg kg-1 for Cd, 0.01 mg kg-1 for Cr, 0.2 mg kg-1 for Cu, 0.03 mg kg-1 for Pb, and 0.09 mg kg-1 for V.

Investigation of a rapid infrared heating assisted mineralization of soybean matrices for trace element analysis.

A fast sample preparation procedure based on use of infrared (IR) assisted heating for mineralization of soybean derived samples has been developed for their subsequent multielement analysis by inductively coupled plasma optical emission spectrometry (ICP-OES) and flame atomic absorption spectrometry (FAAS). A cold finger was examined for refluxing of acid vapors to determine its impact on efficiency and economy of digestion. The optimized procedure, based on 1 g subsamples, 8 mL of HNO3 (65% w/w) and exposure of the mixture to a 500 W IR source for 5 min without refluxing, permitted accurate determination of all analytes in NIST SRM 1568b (rice flour). Detection limits using ICP-OES were (µg/kg) 97, 1.0, 39, 185, 0.47 and 1200 for Ca, Cu, Fe, K, Mn and P, respectively, and 18 for Zn by FAAS. The IR-assisted digestion approach provided a low cost, easy to use system having great potential for implementation in routine analysis of trace elements in soybean and similar matrices.

Comparison between boiling and vacuum cooking (sous-vide) in the bioaccessibility of minerals in bovine liver samples.

Only some of ingested nutrients are available for absorption by the organism. The foods generally are submitted to some heat processing that may interfere in the bioaccessibility of nutrients. There are no studies of the influence of cooking under vacuum (sous vide) on the bioaccessibility of minerals. This study evaluated the in vitro bioaccessibility of Ca, Cu, Fe, K, Mg and Zn in bovine liver samples after traditional cooking in water and using the sous vide procedure. All heat treatments of bovine liver promoted the increase of the bioaccessibility of Ca, Cu, Fe, K and Mg, except for Zn when the effect was the opposite. The sous vide method provided higher bioaccessibility of these minerals than cooking in boiling water, except for K when both methods presented equivalent values. Samples of raw liver and liver cooked using sous vide method presented the following percentage of bioaccessible fraction, respectively: 39.7% and 95.8% (Ca), 8.78% and 26.9% (Cu), 8.80% and 39.5% (Fe), 30.2% and 42.6% (K), 26.4% and 43.9% (Mg), 24.8% and 36.3% (Zn). Thus, under the aspect of improvement availability of studied minerals by organism, the sous-vide technique was the most suitable to cook bovine liver.

A new approach to mineralization of flaxseed (Linum usitatissimum L.) for trace element analysis by flame atomic absorption spectrometry.

A new approach to the analysis of Cu, Fe, Mn and Zn in flaxseed was developed based on infrared-assisted acid digestion. Quantitation by flame atomic absorption spectrometry yields results in agreement with those arising from aggressive total decomposition using conventional microwave-assisted (MW) digestions. A full factorial design in two levels was applied to evaluate the impact of significant variables for all elements to determine optimal experimental conditions. A desirability function revealed these to be: 2.0g sample mass, 8mL of HNO3 and 8min of heating time in the IR system. Precision better than 10% (RSD) was obtained, superior to that of a combined IR-MW approach. Sample preparation based on IR-assisted digestion provides a rapid and inexpensive alternative to other conventional techniques for the analysis of complex samples and is able to accommodate relatively large masses of sample, alleviating potential homogeneity issues as well as enhancing detection power.

Optimization of a cloud point extraction procedure with response surface methodology for the quantification of dissolved iron in produced water from the petroleum industry using FAAS.

The characterization of inorganic elements in the produced water (PW) samples is a difficult task because of the complexity of the matrix. This work deals with a study of a methodology for dissolved Fe quantification in PW from oil industry by flame atomic absorption spectrometry (FAAS) after cloud point extraction (CPE). The procedure is based on the CPE using PAN as complexing agent and Triton X-114 as surfactant. The best conditions for Fe extraction parameters were studied using a Box-Behnken design. The proposed method presented a LOQ of 0.010µgmL-1 and LOD of 0.003µgmL-1. The precision of the method was evaluated in terms of repeatability, obtaining a coefficient of variation of 2.54%. The accuracy of the method was assessed by recovery experiments of Fe spiked that presented recovery of 103.28%. The method was applied with satisfactory performance to determine Fe by FAAS in PW samples.

Development of a wet digestion method for paints for the determination of metals and metalloids using inductively coupled plasma optical emission spectrometry.

Paints, a complex matrix, have a variable composition that is dependent on the application. In this work, a new wet digestion procedure for the determination of Al, As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sn, Sr, Ti and Zn in paint samples using inductively coupled plasma optical emission spectrometry (ICP OES) has been developed. An experimental design approach was employed to determine the optimal conditions for achieving complete solubilization and/or decomposition in the sample preparation method. An efficient sample preparation was developed that consisted of a pre-digestion step at 40°C for 20 min using 1 mL of HNO3 to eliminate organic solvents followed by digestion at 120°C for 3h using 5 mL of HCl and 1 mL of HF in a block digestion. The proposed procedure promotes the complete solubilization of different bases of paints at low temperature and atmospheric pressure. The accuracy was determined by addition/recovery tests and comparing the results with those obtained using the ASTM D335-85a standard sample preparation method. The limits of quantification were 1.78, 0.11, 0.006, 0.006, 0.01, 0.04, 0.006, 0.006, 0.02, 0.07, 0.30, 1.30 and 0.30 mg kg(-1) for Al, As, Ba, Cd, Cr, Cu,Mn, Ni, Pb, Sn, Sr, Ti and Zn, respectively. The proposed method was applied for the analysis of inorganics via the ICP OES of paints with different colors and bases used to cover wall surfaces.