EFFECT OF LIQUID SWINE WASTEWATER DOSES ON PHYSICAL, CHEMICAL AND ELECTROCHEMICAL ATTRIBUTES IN A CERRADO OXISOL. The addition of organic residues enhances soil and plant organic matter and nutrient content. To gauge the impact of varying liquid swine waste (LSW) levels on soil, we studied changes in a clayey Oxisol’s physical, chemical, and electrochemical traits from the Cerrado. LSW doses (0, 50, 150, 450, 600 m3 ha−1) were applied to the 0-0.20 m layer in a randomized design with three replicates. Post a 30-day incubation at 60% field capacity, the soil underwent mineralogical, physical (clay dispersed in water - CDW), chemical (sodium adsorption ratio - SAR, cation exchange capacity - CEC, base saturation - V%), and electrochemical (pH in H2O and KCl, ApH, point of zero charge - PZC, point of zero salt effect - PZSE, surface electric potential - iµo, and electrical conductivity - EC) analyses. The levels of exchangeable Ca, K, Mg, Na, and available P increased with increasing LSW doses. Increasing LSW doses in the soil led to an increase in EC, but soil salinization was not observed at the highest dose. With the application of LSW doses, there was a decrease in pH, ApH, PZSE, and an increase in CEC, PZC and ψo. Despite the increase in ψo, low clay dispersibility was observed. PHYSICAL OXISOL content (LSW Oxisols Oxisol s Cerrado 0, 0 (0 50 150 450 60 ha−1 ha1 ha 1 00.20 0020 0.20 20 0-0.2 replicates 30day day 30 mineralogical CDW, CDW , CDW) sodium SAR CEC V%, V V% V%) pH HO H O KCl ApH PZSE iµo EC analyses Ca K Mg Na dose ψo ( 5 15 45 6 ha− 00 00.2 002 020 0.2 2 0-0. 3 4 00. 02 0. 0-0 0-

The use of materials such as organofunctionalized silica for application in solid phase extraction (SPE) allows the preconcentration of several ions, including Pt, and subsequent detection. This work aims to synthesize and characterize an organofunctionalized silica (Sil-TMSDT) with the silylant N’(trimethoxysilyl)propylethylenetriamine and its application as a solid phase in the preconcentration Pt4+ ions in aqueous media, using detection by flame atomization atomic absorption spectroscopy (FAAS). The Fourier-transform infrared spectroscopy (FTIR) spectra and scanning electron microscopy (SEM) coupled with energy-dispersive spectroscopy (EDS) confirmed the aminofunctionalization of the silica. For the adsorption process, a preconcentration mini-column with 200 mg of Sil-TMSDT, a solution of 0.485 mg L−1 of K2[PtCl6] at pH 10 and HNO3 0.5 mol L−1 as eluent were used, obtaining an enrichment factor of 15-fold with retention efficiency higher than 99%. The Pt4+ ion determined by FAAS showed a linear response between 0.02 and 0.40 mg L−1; a linear coefficient where R = 0.9981; a 16-fold preconcentration factor; a limit of quantification (LOQ) and limit of detection (LOD) of 0.045 and 0.014 mg L−1, respectively. The proposal system showed analytical applicability to determining Pt4+ ion in an aqueous medium and could be used to detect traces of this potentially toxic metal in biological fluids such as urine and blood. SPE (SPE Pt SilTMSDT Sil TMSDT (Sil-TMSDT Ntrimethoxysilylpropylethylenetriamine N trimethoxysilyl propylethylenetriamine Pt4 media FAAS. . (FAAS) Fouriertransform Fourier transform FTIR (FTIR SEM (SEM energydispersive energy dispersive EDS (EDS process minicolumn mini column 20 SilTMSDT, TMSDT, Sil-TMSDT 0485 0 485 0.48 L1 L 1 L− K2PtCl6 KPtCl K2 PtCl6 K PtCl K2[PtCl6 HNO 05 5 0. 15fold fold 15 99 99% 002 02 0.0 040 40 0.4 0.9981 09981 9981 16fold 16 LOQ (LOQ LOD (LOD 0045 045 0.04 0014 014 0.01 respectively blood (FAAS 2 048 48 K2PtCl K2[PtCl 9 00 04 4 0.998 0998 998 004 001 01 0.99 099 0.9 09

The selective separation of precious metals from complex aqueous solutions is important in protecting the environment, aquatic ecosystems, water resources and recycling resources. In this study, cysteine-containing polymeric nanoparticles were synthesized using the molecular imprinting (MIP) technique with the mini-emulsion polymerization method. The basis of the polymer design is inspired by affinity of silver to cysteine in biological systems. The synthesized silver ion imprinted (Ag+-IIP) poly(hydroxyethylmethacrylate-N -methacryloyl-L-cysteine) poly(HEMA-MAC) nanoparticles were characterized by elemental analysis, zeta sizer, Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM). The effects of pH, ionic strength and interaction time on adsorption of Ag+ ions were investigated. In experimental studies, the highest adsorption amount (196.9 mg g1 nanoparticle) was reached in a short period of 40 min at pH 5.0 and 150 mg L-1 concentration. Selectivity studies of synthesized Ag+-IIP nanoparticles against silver (Ag+) ions were carried out in the presence of lithium (Li+), barium (Ba2+), mercury (Hg2+) and cadmium (Cd2+) ions. Experimental results indicate that nanoparticles adsorb Ag+ ions with high selectivity. Ag+-IIP nanoparticles have 3.7, 3.1, 2.4, and 2.6 times more selective or higher affinity for Ag+ ions compared to Li+, Ba2+, Hg2+ and Cd2+ ions, respectively, compared to Ag+-non-imprinted (NIP) nanoparticles. environment ecosystems study cysteinecontaining containing MIP (MIP miniemulsion mini emulsion method systems Ag+IIP AgIIP IIP Ag (Ag+-IIP polyhydroxyethylmethacrylateN poly hydroxyethylmethacrylate N methacryloylLcysteine methacryloyl L -methacryloyl-L-cysteine polyHEMAMAC HEMA MAC poly(HEMA-MAC analysis sizer FTIR (FTIR spectroscopy AFM, AFM , (AFM) SEM. SEM . (SEM) investigated 196.9 1969 196 9 (196. g nanoparticle 4 50 5 0 5. 15 L1 1 L- concentration (Ag+ Li Li+ (Li+) Ba2 Ba Ba2+ (Ba2+) Hg2 Hg (Hg2+ Cd2 Cd (Cd2+ selectivity 37 3 7 3.7 31 3.1 24 2 2.4 26 6 2. respectively Ag+nonimprinted Agnonimprinted non NIP (NIP (AFM (SEM 196. 19 (196 (Ag (Li+ (Ba2+ (Hg2 (Cd2 3. nonimprinted (19 (Li (Ba2 (Hg (Cd (1 (Ba (

In the water/triethanolamine/ethanol system, TiCl4 aqueous solution is used as the precursor to regulate the conversion rate of TiCl4 by changing the reaction temperature, water volume, pH value, and ethanol amount. The experiment uses a single-factor method to investigate the dynamic relationship between Ti4+ concentration and time under various factors, thereby achieving controllable TiO2 production. The experimental results showed that under a single factor, the conversion rate showed a trend of first steep and then slow growth within 180 min. After 180 min, the conversion rate tended to stabilize. Considering various factors, it was found that VTiCl4:VC6H15NO3:VH2O:VC2H5OH = 1:6:15:30, pH = 7, reaction time at room temperature was 4 h, and the hydrolysis effect was good. The final conversion rate was 90.46%, and the hydrolysis reaction conforms to the first-order reaction equation. Kinetic parameters: pre-factor (A) = 0.107, activation energy (Ea) = 4488.65 J mol-1. watertriethanolamineethanol triethanolamine system TiCl volume value amount singlefactor factor Ti4 Ti factors TiO production 18 min stabilize VTiCl4VC6H15NO3VH2OVC2H5OH VTiClVCHNOVHOVCHOH VTiCl4 VC6H15NO3 VH2O VC2H5OH VTiCl VC H NO VH O OH 161530, 161530 1 6 15 30, 30 1:6:15:30 7 h good 9046 90 46 90.46% firstorder order equation parameters prefactor pre A (A 0107 0 107 0.107 Ea (Ea 448865 4488 65 4488.6 mol1. mol1 mol 1. mol-1 OVC VCHNO VC6H15NO VHO VCHOH 16153 3 1:6:15:3 904 9 90.46 010 10 0.10 44886 448 4488. mol- 1615 1:6:15: 90.4 01 0.1 44 161 1:6:15 90. 0. 16 1:6:1 1:6: 1:6 1:

ABSTRACT Proper waste management is a major worldwide concern; waste is disposed of directly into the environment, affecting water, soil and air quality. The development and production of green energy sources is strongly encouraged in modern society. The aim of this study, in accordance with Sustainable Development Goals (SDGs) 1, 2 and 7 of the 2030 Agenda of the UN, is to combine the correct disposal of animal waste with the generation of energy to mitigate the energy insecurity of families in an extremely vulnerable semi-arid region in the north-east of the country using biodigesters. To this end, a conceptual proposal was drawn up for a low-cost, easy-to-maintain and easy-to-use biodigester. A small-scale prototype was used to assess its operation by evaluating the main factors that affect biogas production (pH, temperature and the biomass properties: total solids, fixed solids, volatile solids, concentration of volatile fatty acids and C/N ratio). Evaluation of the test prototype gave satisfactory results that corroborate other studies and make it possible to propose an economically viable and efficient full-scale biodigester for biogas production. concern environment water quality society study SDGs (SDGs 1 203 UN semiarid semi arid northeast north east biodigesters end lowcost, lowcost low cost, cost low-cost easytomaintain easy maintain easytouse use smallscale small scale pH, pH (pH properties solids CN C N ratio. ratio . ratio) fullscale full 20

RESUMO: O objetivo deste trabalho foi extrair lignina de Eucalyptus sp. licor negro kraft e avaliar a influência de sua adição nas propriedades do adesivo lignina-fenol-formaldeído. Os adesivos foram sintetizados em diferentes porcentagens de massa de fenol por lignina, denominados adesivos lignina-fenol-formaldeído nas proporções de 25, 30, 50, 75 e 80%. Os parâmetros avaliados nos adesivos foram pH, teor de sólidos totais, teor de compostos orgânicos, teor de compostos inorgânicos, tempo de gelatinização e comportamento do adesivo na linha de cola. O pH variou de 10,63 a 11,65. Para o teor de sólidos totais foi encontrado o valor de 53 a 69%. Os teores de compostos orgânicos variaram de 51 a 75% e de inorgânicos de 25 a 49%. Observou-se que com a adição da macromolécula na formulação do adesivo, o teor de sólidos totais e orgânicos foi reduzido proporcionalmente enquanto o de sólidos inorgânicos foi elevado. O tempo de gelatinização foi reduzido devido à adição de lignina. As menores proporções de adição apresentaram melhor penetração e fluidez na interface com a madeira. A lignina kraft extraída do licor negro kraft de eucalipto é um ótimo adesivo com potencial para substituir parcialmente o fenol derivado do petróleo, com grande potencial para uso e aplicação nos setores aeronáutico e automotivo, no processo de colagem de peças estruturais. RESUMO sp ligninafenolformaldeído. ligninafenolformaldeído formaldeído. formaldeído 30 50 7 80 80% cola 1063 10 63 10,6 1165 11 65 11,65 5 69 69% 2 49 49% Observouse Observou se elevado madeira petróleo automotivo estruturais 3 8 106 1 6 10, 116 11,6 4 11,

ABSTRACT: The objective of this research was to extract lignin from Eucalyptus sp. kraft black liquor and to evaluate the influence of its addition on the properties of the lignin-phenol-formaldehyde adhesive. The adhesives were synthesized at different phenol mass percentages by lignin, called lignin-phenol-formaldehyde adhesives in the proportions of 25, 30, 50, 75 and 80%. The parameters evaluated in the adhesives were pH, total solid content, organic compound content, inorganic compound content, gelatinization time and adhesive behavior in the glue line. The pH ranged from 10.63 to 11.65. For the total solid content was found the value of 53 to 69 %. The contents of organic compounds ranged from 51 to 75% and inorganic from 25 to 49%. It was observed that with the addition of macromolecule in the adhesive formulation, the total and organic solid content was reduced proportionally while the inorganic solid was high. The gelatinization time was reduced due to the addition of lignin. The lower proportions of addition presented better penetration and fluidity in interface with the wood. The kraft lignin extracted from eucalyptus kraft black liquor is a great adhesive with potential to partially replace petroleum-derived phenol, with great potential for use and application in the aeronautical and automotive sectors, in the bonding process of structural parts. ABSTRACT sp ligninphenolformaldehyde formaldehyde 30 50 7 80 80% line 1063 10 63 10.6 1165 11 65 11.65 5 6 % 2 49 49% formulation high wood petroleumderived petroleum derived sectors parts 3 8 106 1 10. 116 11.6 4 11.

This study expands and shows the versatility of applications in hydrophilic interaction chromatography coupled with triple quadrupole mass spectrometry (HILIC-MS/MS) using a FRULIC-N column to determine 31 phenolic compounds in beverage industry residues (coffee, apple juice, beer, and wine). Optimization, via Doehlert design, determined the acetonitrile proportion (50-90%) and pH (3.0-7.0) in the mobile phase (MP). A 22 factorial design assessed the concentration of ammonium acetate (10-110 mmol L-1) in the MP and column temperature (20-60 °C). Injection volume (5-45 µL) was univariately optimized. Separations at 60 °C reduced chromatographic run time to less than 11 min. Gradient elution (500 µL min-1) employed an MP comprising acetonitrile and ammonium acetate (110 mmol L-1, pH 7). Validation demonstrated average coefficient of determination (R2) 0.9707, limit of detection 0.001-0.503 mg L-1 and quantification 0.004-1.524 mg L-1, precision < 12.2%, recovery 92.4-110.8%. The method was applied to five residues, indicating its viability for determining phenolics in beverage production residues. HILICMS/MS HILICMSMS HILIC MS/MS MS (HILIC-MS/MS FRULICN FRULIC N 3 coffee, coffee (coffee juice beer wine. wine . wine) Optimization 5090% 5090 50 90% 90 (50-90% 3.07.0 3070 3.0 7.0 0 7 (3.0-7.0 MP. (MP) 2 10110 10 110 (10-11 L1 L 1 2060 20 (20-6 °C. C °C) 545 5 45 (5-4 optimized 6 min 500 (50 min1 min-1 (11 L1, 1, 7. 7) R2 R (R2 09707 9707 0.9707 0.0010.503 00010503 0.001 0.503 001 503 0.001-0.50 L- 0.0041.524 00041524 0.004 1.524 004 524 0.004-1.52 122 12 12.2% 92.4110.8%. 9241108 92.4 110.8%. 92 4 8 92.4-110.8% HILICMS MSMS 509 9 (50-90 07 3.07. 307 30 3. 70 (3.0-7. (MP 1011 (10-1 206 (20- 54 (5- (5 min- (1 (R 0970 970 0.970 0010 0.0010.50 0001050 0001 0.00 0503 0.50 00 0.001-0.5 0041 0.0041.52 0004152 0004 1524 1.52 52 0.004-1.5 12.2 4110 92.4110.8% 924110 924 92. 1108 110.8% 92.4-110.8 (50-9 3.07 (3.0-7 101 (10- (20 ( 097 97 0.97 0.0010.5 000105 000 0.0 050 0.5 0.001-0. 0.0041.5 000415 152 1.5 0.004-1. 12. 411 92.4110.8 92411 110.8 92.4-110. (50- (3.0- (10 (2 09 0.9 0.0010. 00010 0. 05 0.001-0 0.0041. 00041 15 1. 0.004-1 41 92.4110. 9241 110. 92.4-110 (3.0 0.0010 0.001- 0.0041 0.004- 92.4110 92.4-11 (3. 92.411 92.4-1 (3 92.41 92.4-

RESUMO O pimentão, cultura de importância nutricional, destaca-se por seu valor de vitamina C. Diante da necessidade de práticas agrícolas sustentáveis, o estudo explorou o uso de biocarvões derivados de resíduos regionais como alternativa na cultura de pimentão. Nesse contexto, objetivou-se avaliar o efeito de biocarvões provenientes de cama de frango, fibra de coco e palha de arroz, nas características biométricas e físico-químicas de frutos de pimentão verde, na produção de frutos por planta e na produtividade. A pesquisa foi conduzida em campo no delineamento em blocos casualizados, em esquema fatorial 5 × 3 + 1, referentes a cinco doses de biocarvão (0, 3, 6, 9 e 12 t ha-1) e três tipos de biocarvão (fibra de coco, cama de aviário e palha de arroz) com quatro repetições, mais um tratamento adicional (adubação mineral). Foram avaliadas variáveis biométricas (comprimento e diâmetro dos frutos, espessura da casca, número de frutos, massa do fruto) e físico-químicas dos frutos (sólidos solúveis, acidez titulável, pH, vitamina C e teor de cinzas), produção e produtividade dos frutos. A produção de frutos de pimentão verde não foi influenciada pelos biocarvões, porém as doses de biocarvões influenciaram todas as variáveis analisadas com exceção da espessura da casca. Os teores de vitamina C e de sólidos solúveis foram maiores nos tratamentos com biocarvões e menores com adubação mineral. A maior influência na acidificação dos frutos foi com o biocarvão produzido com palha de arroz. nutricional destacase destaca se sustentáveis contexto objetivouse objetivou frango arroz físicoquímicas físico químicas casualizados 1 0, 0 (0 6 ha1 ha ha-1 repetições mineral . mineral) comprimento casca fruto titulável pH cinzas, cinzas , cinzas) ( ha-

ABSTRACT Bell pepper, a crop of nutritional importance, stands out for its vitamin C content. Given the need for sustainable agricultural practices, the present study explored the use of biochars derived from regional waste as an alternative in bell pepper cultivation. In this context, the present study aimed to evaluate the effect of biochars from poultry litter, coconut fiber, and rice straw on the biometric and physicochemical characteristics of bell pepper fruits, on fruit production per plant and on fruit yield. The experiment was performed in the field in a randomized block design, in a 5 × 3 + 1 factorial scheme, referring to five doses of biochar (0, 3, 6, 9, and 12 t ha-1) and three types of biochar (coconut fiber, poultry litter, and rice straw) with four repetitions, plus an additional treatment (mineral fertilization). Biometric variables (fruit length and diameter, skin thickness, number of fruits, fruit mass) and physicochemical variables of the fruits (soluble solids, titratable acidity, pH, vitamin C, and ash content), production and yield of the fruits were evaluated. The production of bell pepper fruits was not influenced by biochars, but the doses of biochars influenced all variables analyzed with the exception of skin thickness. Vitamin C and soluble solids contents were higher in treatments with biochar and lower with mineral fertilizer. Biochar produced from rice straw had the greatest influence on fruit acidification. importance content practices cultivation context litter fiber design scheme 0, 0 (0 6 9 ha1 ha ha-1 repetitions fertilization. fertilization . fertilization) diameter thickness mass acidity pH content, , content) evaluated fertilizer acidification ( ha-

RESUMO A estruvita (NH4MgPO4∙6H2O) é um fertilizante de liberação lenta obtido através da recuperação de fósforo e/ou nitrogênio de águas residuais geralmente pela adição de sais de magnésio. Neste sentido, objetivou-se avaliar a viabilidade da substituição de fontes comerciais de magnésio por fontes alternativas no processo de precipitação de estruvita, em termos de remoção de amônio e fosfato, e quantificação e caracterização do cristal precipitado. Os experimentos foram conduzidos em escala de bancada sob delineamento inteiramente casualizado a pH 9,5 através da precipitação de uma solução de efluente sintético com quatro diferentes fontes de magnésio: MgCl2∙6H2O, MgSO4∙7H2O, MgO e magnesita (MgCO3). Após pré-acidificação, soluções derivadas de fontes alternativas de baixo custo de magnésio removeram acima de 55 e 90% de nitrogênio amoniacal e fosfato em solução, respectivamente, e alcançaram por volta de 10 g L-1 de cristais precipitados. A proximidade dos resultados obtidos com soluções derivadas de fontes comerciais de magnésio (46ꟷ56% de remoção de nitrogênio amoniacal, 97% de remoção de fosfato, e mais de 6 g L-1 de precipitado formado) indicou que reagentes alternativos puderam facilmente substituir os comerciais se submetidos ao prévio processo de digestão, a fim de tornar o magnésio disponível em solução. A análise qualitativa por difratometria de raios-X confirmou a presença de estruvita e newberyita na maioria dos precipitados. NH4MgPO4∙6H2O NH4MgPO46H2O NHMgPOHO NH4MgPO4 6H2O NH MgPO H O (NH4MgPO4∙6H2O eou ou sentido objetivouse objetivou 95 9 5 9, MgCl26H2O MgClHO MgCl2 MgCl MgCl2∙6H2O MgSO47H2O MgSOHO MgSO4 7H2O MgSO MgSO4∙7H2O MgCO3. MgCO3 MgCO . (MgCO3) préacidificação, préacidificação pré acidificação, acidificação pré-acidificação 90 respectivamente 1 L1 L L- precipitados 46ꟷ56% 46ꟷ56 ꟷ (46ꟷ56 97 formado digestão raiosX raios X NHMgPO NH4MgPO HO (MgCO3 46ꟷ5 (46ꟷ5 (MgCO 46ꟷ (46ꟷ

ABSTRACT Struvite (NH4MgPO4∙6H2O) is a slow-release fertilizer obtained through phosphorus and/or nitrogen recovery from wastewaters, usually by adding magnesium salts. In this sense, the aim was to evaluate the viability of replacing commercial magnesium sources with alternative ones in the struvite precipitation process regarding ammonium and phosphate removal and precipitated crystal quantification and characterization. Experiments were conducted on a bench scale in a completely randomized design at pH 9.5 by precipitation of synthetic wastewater solution with four magnesium sources: MgCl2∙6H2O, MgSO4∙7H2O, MgO, and magnesite (MgCO3). After pre-acidification, derived solutions from low-cost alternative sources of magnesium removed above 55 and 90% of ammonium nitrogen and phosphate in solution, respectively, and reached around 10 g L-1 of precipitated crystals. Results proximity obtained with solutions derived from commercial sources of magnesium (46ꟷ56% of ammonium nitrogen removal, 97% of phosphate removal, and more than 6 g L-1 of precipitate formed) indicated that alternative reagents could easily substitute commercial ones if submitted to the previous digestion process, making magnesium available in solution. Qualitative analysis by X-ray diffraction confirmed the presence of both struvite and newberyite in most precipitates. NH4MgPO4∙6H2O NH4MgPO46H2O NHMgPOHO NH4MgPO4 6H2O NH MgPO H O (NH4MgPO4∙6H2O slowrelease slow release andor or wastewaters salts sense characterization 95 9 5 9. MgCl26H2O MgClHO MgCl2 MgCl MgCl2∙6H2O MgSO47H2O MgSOHO MgSO4 7H2O MgSO MgSO4∙7H2O MgO MgCO3. MgCO3 MgCO . (MgCO3) preacidification, preacidification pre acidification, acidification pre-acidification lowcost low cost 90 respectively 1 L1 L L- crystals 46ꟷ56% 46ꟷ56 ꟷ (46ꟷ56 97 formed Xray X ray precipitates NHMgPO NH4MgPO HO (MgCO3 46ꟷ5 (46ꟷ5 (MgCO 46ꟷ (46ꟷ

In the present study a spectrophotometric method for Cr(VI) determination in organic fertilizers, especially those from tanning industry residues, is proposed. Conditions for chromium extraction, extract clean-up and analytical characteristics of the method were established. The method is based on the complexation of Cr(VI) with 1,5-diphenylcarbazide (DPC) in acid medium (pH 2.0). A mixture of NaOH and Na2CO3 solution at 0.125 and 0.07 mol L–1 (pH 12), respectively, and heating at 90 °C for 60 min were the best conditions for chromium extraction. Florisil and activated charcoal were tested for clean-up of the extract, with activated charcoal being effective. Under the established conditions, the calibration linear range is up to 2500 μg L–1 Cr(VI), the results obtained are in agreement with the value of a certified reference material (CRM041), precision is better than 5% for five consecutive determinations of a solution at 1000 μg L–1 of Cr(VI) and the limit of quantification is 1.62 μg g–1. In can be concluded that the method is robust, accurate and precise, and can be easily applied for the determination of Cr(VI) in routine analysis, since it complies with legislation of most countries regarding the maximum allowed concentration of 2 μg g–1 of Cr(VI). CrVI Cr VI Cr(VI fertilizers residues proposed extraction cleanup clean 1,5diphenylcarbazide 15diphenylcarbazide diphenylcarbazide 1,5 1 5 DPC (DPC pH 2.0. 20 2.0 . 0 2.0) NaCO Na CO Na2CO 0125 125 0.12 007 07 0.0 L1 L L– 12, 12 , 12) respectively 9 C 6 effective 250 CrVI, CRM041, CRM041 CRM (CRM041) 100 162 62 1.6 g1 g robust precise analysis g– CrVI. 5diphenylcarbazide 15 1, 2. 012 0.1 00 0. 25 CRM04 (CRM041 10 16 1. 01 CRM0 (CRM04 (CRM0 (CRM

Two poly(acrylic acid-b-acrylamide) copolymers, and a poly(acrylic acid) homopolymer were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization and tested for nickel removal from aqueous media. RAFT was used for better interchain composition homogeneity and to facilitate the synthesis of the block copolymers. Liquid-phase polymer-based retention (LPR) was used to compare the nickel binding capacity. Uptake tests were carried out at pH 3.0, 4.0, and 5.0. Nickel adsorption isotherms in the range of 1 to 7 mmol L−1 were achieved and the Langmuir adsorption model was applied. Maximum binding capacity (Qm) of Ni2+ at 298 K depended on the composition of the copolymers and pH. The polyacid block (PAA) was the major structural feature responsible for high values of nickel binding. All materials presented better uptake at higher pH, probably due to polyacid deprotonation and the increase in the electrostatic interactions. Up to approximately 100 mg of nickel per gram of homopolymer could be retained at pH = 5.0. Even though the presence of a poly(acrylamide) block decreases the binding capacity compared to PAA, that block has a specific contribution to nickel binding and can also provide better features to the material as better solubilization, and others. polyacrylic poly acrylic acidbacrylamide acid b acrylamide acid-b-acrylamide additionfragmentation addition fragmentation (RAFT media Liquidphase Liquid phase polymerbased polymer based LPR (LPR 30 3 0 3.0 40 4 4.0 50 5 5.0 L1 L L− applied Qm (Qm Ni2 Ni 29 PAA (PAA interactions 10 polyacrylamide poly(acrylamide solubilization others 3. 4. 5. 2

This research aims to develop a precise and efficient dispersive solid-phase microextraction (DSPE) technique using third-generation polyamidoamine (PAMAM) dendrimer-grafted nanoparticles to quantify benzoylurea pesticides in green tea, black tea, and oolong tea infusions. The extraction efficiency is optimized through single-factor adjustments of key parameters, including adsorbent quantity (5-20 mg), adsorption duration (5-20 min), desorbent identity (methanol, acetonitrile), volume (100-600 μL), sodium chloride concentration (0-10%, m/v), and sample solution pH (3-8). The optimized method demonstrates linearity in the range of 2-500 μg L-1, with limits of detection (LODs) ranging from 0.6-1.5 μg L-1 and limits of quantification (LOQs) from 2.0 5.0 μg L-1. Recovery rates of 81.2-96.0% are achieved, with intra-day relative standard deviations (RSDs) of 1.4-2.8% and inter-day relative standard deviations of 2.0-3.9%, indicating high accuracy and repeatability. The successful application of detecting residues in commercial tea samples underscores the strong potential of the technique to determine benzoylurea analyte levels. solidphase solid phase DSPE (DSPE thirdgeneration third generation PAMAM (PAMAM dendrimergrafted dendrimer grafted infusions singlefactor single factor parameters 520 5 20 (5-2 mg, mg , mg) min, min min) methanol, methanol (methanol acetonitrile, acetonitrile acetonitrile) 100600 100 600 (100-60 μL, μL μL) 010%, 010 0 10%, 10 (0-10% m/v, mv m/v m v m/v) 38. 38 3 8 . (3-8) 2500 2 500 2-50 L1, L1 L 1, 1 LODs (LODs 0.61.5 0615 0.6 1.5 6 0.6-1. L- LOQs (LOQs 2. 50 5. L1. 1. 81.296.0% 812960 81.2 96.0% 81 96 81.2-96.0 achieved intraday intra day RSDs (RSDs 1.42.8% 1428 1.4 2.8% 4 1.4-2.8 interday inter 2.03.9%, 2039 3.9%, 9 2.0-3.9% repeatability levels 52 (5- 10060 60 (100-6 010% 01 10% (0-10 (3-8 250 2-5 61 0.61. 061 06 0. 15 0.6-1 296 81.296.0 81296 812 81. 960 96.0 81.2-96. 42 1.42.8 142 14 28 2.8 1.4-2. 03 2.03.9% 203 39 3.9% 2.0-3.9 (5 1006 (100- (0-1 (3- 25 2- 0.61 0.6- 29 81.296. 8129 96. 81.2-96 1.42. 1.4-2 2.03.9 3.9 2.0-3. ( (100 (0- (3 81.296 81.2-9 1.42 1.4- 2.03. 3. 2.0-3 (10 (0 81.29 81.2- 2.03 2.0- (1

Bulk precipitation (BP) samples were collected at two coastal urban sites and two montane Atlantic Forest (400 and 1000 m altitude) areas in southeastern Brazil from August 2008 to August 2009. These samples were analyzed for the major inorganic ions (H+, Na+, K+, Ca2+, Mg2+, Cl- and SO42-) found in rainwater. The concentrations of inorganic nitrogen species (NH4+, NO3- and NO2-) were compiled from a previous study. The volume-weighted mean (VWM) concentrations of inorganic ions differed spatially, with higher values at the coastal urban and coastal periurban sites. On a molar basis, Cl- and Na+ together comprised 60% of the total inorganic constituents at the coastal urban site and 34-42% at the other three sites, as it is the closest to the ocean. Magnesium was also primarily associated with sea-salt aerosol. Non-sea-salt (nss) fractions of K+, Ca2+ and SO42- comprised 68-93% of their VWM concentrations, indicating the contribution of natural (mostly biogenic) and anthropogenic (SO2 oxidation for the latter) sources. Finally, we found that the acidity of BP at the four sampling sites is primarily controlled by the NH4+, nss-Ca2+, nss-SO42-, and NO3- ions, resulting in VWM pH values ranging from 5.60 (lower montane forest) to 5.98 (coastal periurban site). (BP 400 (40 100 altitude 200 2009 H+, H (H+ Na K K+ Ca2 Ca Mg2 Mg Mg2+ Cl SO42 SO rainwater NH4 NH (NH4+ NO3 NO NO2 NO2- study volumeweighted volume weighted (VWM spatially basis 60 3442% 3442 34 42% 42 34-42 ocean seasalt sea salt aerosol Nonseasalt Non nss (nss 6893% 6893 68 93% 93 68-93 mostly biogenic SO2 (SO latter sources Finally NH4+ nssCa2+, nssCa2 nssCa nss-Ca2+ nssSO42, nssSO42 nssSO , nss-SO42- 560 5 5.6 lower forest 598 98 5.9 site. . site) 40 (4 10 20 H+ (H SO4 (NH4 6 344 3 4 34-4 689 9 68-9 nssCa2+ nss-Ca2 nssSO4 nss-SO42 56 5. 59 ( 1 2 (NH 34- 68- nss-Ca nss-SO4 nss-SO

Sensor calibration for dissolved gas is a critical and necessary step to ensure consistent sensor response over time and under different conditions. In this work, we describe a 3D printed device that facilitates the calibration of gas sensors. The device effectively maintained gas concentration in the solution for at least 2 h. Analytical curves were constructed in the pH range of 2 to 12, yielding determination coefficients surpassing 0.98. The chosen method proved suitable for the calibration of the sensors. Furthermore, using accurate and reliable reference sensors contributed to obtaining precise and trustworthy measurements. conditions work D h 12 098 0 98 0.98 Furthermore measurements 1 09 9 0.9 0.

A green supramolecular vortex-assisted microextraction employing a mixture of 1-decanol and tetrahydrofuran (THF) was developed for the simultaneous extraction of pesticides from different classes (insecticides, fungicides, and herbicides) from water and flour samples, followed by their determination in high-performance liquid chromatography with diode array detector (HPLC-DAD). The most favorable results were achieved at pH 6.0 in the presence of 4% (m/v) NaCl, utilizing a low volume of 1-decanol and THF (75 and 400 µL, respectively), a short vortex-assisted extraction time (120 s), and centrifugation time (120 s). These conditions yielded high preconcentration factors ranging from 50.1 to 90.3 and low limits of quantification (LOQs) ranging from 1.3 to 27.3 µg L-1. The intraday (n = 10) and interday (n =1 0) precision, assessed as the percentage of relative standard deviation (RSD), varied from 4.4 to 12.4%. The optimized method was successfully applied to determine the pesticides in water and flour samples, with recoveries ranging from 81 to 111%. vortexassisted vortex assisted 1decanol decanol 1 (THF insecticides, insecticides (insecticides fungicides herbicides samples highperformance performance HPLCDAD. HPLCDAD HPLC DAD . (HPLC-DAD) 60 6 0 6. 4 m/v mv m v (m/v NaCl 75 (7 40 µL respectively, respectively , respectively) 120 (12 s, s s) s. 501 50 50. 903 90 3 90. LOQs (LOQs 13 1. 273 27 27. L1. L1 L L-1 n 10 precision RSD, RSD (RSD) 44 4. 124 12 12.4% 8 111 111% (HPLC-DAD 7 ( (1 5 9 2 L- (RSD 12.4 11 12.