Interest of qualitative and quantitative profiling of endocannabinoids for evaluation of their implication in drug addiction process

Introduction: In the middle of the 90's, the discovery of endogenous ligands for cannabinoid receptors opened a new era in this research field. Amides and esters of arachidonic acid have been identified as these endogenous ligands. Arachidonoylethanolamide (anandamide or AEA) and 2-Arachidonoylglycerol (2-AG) seem to be the most important of these lipid messengers. In addition, virodhamine (VA), noladin ether (2-AGE), and N-arachidonoyl dopamine (NADA) have been shown to bind to CB receptors with varying affinities. During recent years, it has become more evident that the EC system is part of fundamental regulatory mechanisms in many physiological processes such as stress and anxiety responses, depression, anorexia and bulimia, schizophrenia disorders, neuroprotection, Parkinson disease, anti-proliferative effects on cancer cells, drug addiction, and atherosclerosis. Aims: This work presents the problematic of EC analysis and the input of Information Dependant Acquisition based on hybrid triple quadrupole linear ion trap (QqQLIT) system for the profiling of these lipid mediators. Methods: The method was developed on a LC Ultimate 3000 series (Dionex, Sunnyvale, CA, USA) coupled to a QTrap 4000 system (Applied biosystems, Concord, ON, Canada). The ECs were separated on an XTerra C18 MS column (50 × 3.0 mm i.d., 3.5 μm) with a 5 min gradient elution. For confirmatory analysis, an information-dependant acquisition experiment was performed with selected reaction monitoring (SRM) as survey scan and enhanced produced ion (EPI) as dependant scan. Results: The assay was found to be linear in the concentration range of 0.1-5 ng/mL for AEA, 0.3-5 ng/mL for VA, 2-AGE, and NADA and 1-20 ng/mL for 2-AG using 0.5 mL of plasma. Repeatability and intermediate precision were found less than 15% over the tested concentration ranges. Under non-pathophysiological conditions, only AEA and 2-AG were actually detected in plasma with concentration ranges going from 104 to 537 pg/mL and from 2160 to 3990 pg/mL respectively. We have particularly focused our scopes on the evaluation of EC level changes in biological matrices through drug addiction and atherosclerosis processes. We will present preliminary data obtained during pilot study after administration of cannabis on human patients. Conclusion: ECs have been shown to play a key role in regulation of many pathophysiological processes. Medical research in these different fields continues to growth in order to understand and to highlight the predominant role of EC in the CNS and peripheral tissues signalisation. The profiling of these lipids needs to develop rapid, highly sensitive and selective analytical methods.

Validation of hepcidin quantification in plasma using LC-HRMS and discovery of a new hepcidin isoform.

BACKGROUND: Hepcidin, a 25 amino acid peptide, plays an important role in iron homeostasis. Some hepcidin truncated peptides have antibiotic effects. RESULTS: A new analytical method for hepcidin determination in human plasma using LC-HRMS operating in full-scan acquisition mode has been validated. The extraction consists of protein precipitation and a drying reconstitution step; a 2.1 x 50 mm (idxL) C18 analytical column was used. Detection specificity, stability, accuracy, precision and recoveries were determined. The LOQ/LOD were 0.25/0.1 nM, respectively. More than 600 injections of plasma extracts were performed, allowing evaluation of the assay robustness. Hepcidin-20, hepcidin-22 and a new isoform, hepcidin-24, were detected in patients. CONCLUSION: The data underscore the usefulness of LC-HRMS for in-depth investigations related to hepcidin levels and pathways.

Characterization of Aspergillus species based on fatty acid profiles

Cellular fatty acid (FA) composition was utilized as a taxonomic tool to discriminate between different Aspergillus species. Several of the tested species had the same FA composition and different relative FA concentrations. The most important FAs were palmitic acid (C16:0), estearic acid (C18:0), oleic acid (C18:1) and linoleic acid (C18:2), which represented 95% of Aspergillus FAs. Multivariate data analysis demonstrated that FA analysis is a useful tool for differentiating species belonging to genus Aspergillus. All the species analyzed showed significantly FA acid profiles (p < 0.001). Furthermore, it will be possible to distinguish among Aspergillus spp. in the Flavi Section. FA composition can serve as a useful tool for the identification of filamentous fungi.

Determinació d'hidrocarburs aromàtics policíclics (PAHs) en mostres de sòls per cromatografia de gasos acoblada a l'espectrometria de masses (GC/MS)

La importància dels Hidrocarburs Aromàtics Policíclics (PAHs) com a contaminants ha estat sempre en debat. Des del moment en què no compleixen els requeriments de persistència, toxicitat i transport a llargues distàncies, no es consideren contaminants orgànics persistents (POPs). En conseqüència, no es troben inclosos dins la llista dels dirty dozen de la Convenció d’Estocolm sobre POPs. A més, ja que el seu alliberament no és intencionat, algunes veus han plantejat la possibilitat d’eliminar o reduir la quantitat d’aquests compostos a l’atmosfera i que arriben també, per deposició, al sòl, sediments, aigües, etc. Tanmateix, segons el Protocol firmat pel Comitè Estats Units-Europa (UNECE), els PAHs haurien d’haver estat inclosos a aquesta llista ja que són productes químics les emissions dels quals haurien de ser minimitzades o previngudes. És per això i l’interès pel medi ambient que dins el projecte Estudi de la influència de contaminants orgànics (BTEX i PAHs) en la mobilitat de metalls pesants en sòls, al qual es vol entendre quin és el mecanisme de transport dels metalls pesants en presència d’aquests contaminants, enfocat sobretot als marges de les carreteres per la combustió de gasolines i l’exhaust dels vehicles, que es justifica aquest treball de recerca. Aquest treball de recerca es basa en la posta a punt d’un mètode d’anàlisi de PAHs mitjançant la Cromatografia de Gasos acoblada a l’Espectrometria de Masses (GC/MS). Cadascun dels mètodes seguits estan reportats a la Environmental Protection Agency dels Estats Units (US EPA), però tot i així cal fer la optimització, realitzant o no, lleus modificacions d’aquests per ajustar-nos a les nostres necessitats específiques. En aquest treball de recerca s’exposen els diferents passos a realitzar un cop feta la presa de mostra fins l’expressió final dels resultats un cop identificats i quantificats els PAHs d’interès presents en una matriu de sòl. Això comprèn la seva extracció inicial mitjançant el Soxhlet, un cleanup posterior a partir tant de l’extracció en fase sòlida (SPE) amb una fase C18 com la cromatografia en columna utilitzant gel de sílice com a adsorbent. Finalment, s’han determinat els paràmetres influents en la separació, identificació i quantificació dels PAHs amb relació a la cromatografia de gasos i la seva detecció per espectrometria de masses.

Quantification of 4 antidepressants and a metabolite by LC-MS for therapeutic drug monitoring.

A liquid chromatography method coupled to mass spectrometry was developed for the quantification of bupropion, its metabolite hydroxy-bupropion, moclobemide, reboxetine and trazodone in human plasma. The validation of the analytical procedure was assessed according to Société Française des Sciences et Techniques Pharmaceutiques and the latest Food and Drug Administration guidelines. The sample preparation was performed with 0.5mL of plasma extracted on a cation-exchange solid phase 96-well plate. The separation was achieved in 14min on a C18 XBridge column (2.1mm×100mm, 3.5μm) using a 50mM ammonium acetate pH 9/acetonitrile mobile phase in gradient mode. The compounds of interest were analysed in the single ion monitoring mode on a single quadrupole mass spectrometer working in positive electrospray ionisation mode. Two ions were selected per molecule to increase the number of identification points and to avoid as much as possible any false positives. Since selectivity is always a critical point for routine therapeutic drug monitoring, more than sixty common comedications for the psychiatric population were tested. For each analyte, the analytical procedure was validated to cover the common range of concentrations measured in plasma samples: 1-400ng/mL for reboxetine and bupropion, 2-2000ng/mL for hydroxy-bupropion, moclobemide, and trazodone. For all investigated compounds, reliable performance in terms of accuracy, precision, trueness, recovery, selectivity and stability was obtained. One year after its implementation in a routine process, this method demonstrated a high robustness with accurate values over the wide concentration range commonly observed among a psychiatric population.

Generic approach for the sensitive absolute quantification of large undigested peptides in plasma using a particular liquid chromatography-mass spectrometry setup.

A generic LC-MS approach for the absolute quantification of undigested peptides in plasma at mid-picomolar levels is described. Nine human peptides namely, brain natriuretic peptide (BNP), substance P (SubP), parathyroid hormone 1-34 (PTH), C-peptide, orexines A and B (Orex-A and -B), oxytocin (Oxy), gonadoliberin-1 (gonadothropin releasing-hormone or luteinizing hormone-releasing hormone, LHRH) and α-melanotropin (α-MSH) were targeted. Plasma samples were extracted via a 2-step procedure: protein precipitation using 1vol of acetonitrile followed by ultrafiltration of supernatants on membranes with a MW cut-off of 30 kDa. By applying a specific LC-MS setup, large volumes of filtrates (e.g., 2×750 μL) were injected and the peptides were trapped on a 1mm i.d.×10 mm length C8 column using a 10× on-line dilution. Then, the peptides were back-flushed and a second on-line dilution (2×) was applied during the transfer step. The refocalized peptides were resolved on a 0.3mm i.d. C18 analytical column. Extraction recovery, matrix effect and limits of detection were evaluated. Our comprehensive protocol demonstrates a simple and efficient sample preparation procedure followed by the analysis of peptides with limits of detection in the mid-picomolar range. This generic approach can be applied for the determination of most therapeutic peptides and possibly for endogenous peptides with latest state-of-the-art instruments.

Quantification of typical antipsychotics in human plasma by ultra-high performance liquid chromatography tandem mass spectrometry for therapeutic drug monitoring.

A selective and sensitive method was developed for the simultaneous quantification of seven typical antipsychotic drugs (cis-chlorprothixene, flupentixol, haloperidol, levomepromazine, pipamperone, promazine and zuclopenthixol) in human plasma. Ultra-high performance liquid chromatography (UHPLC) was used for complete separation of the compounds in less than 4.5min on an Acquity UPLC BEH C18 column (2.1mm×50mm; 1.7μm), with a gradient elution of ammonium formate buffer pH 4.0 and acetonitrile at a flow rate of 400μl/min. Detection was performed on a tandem quadrupole mass spectrometer (MS/MS) equipped with an electrospray ionization interface. A simple protein precipitation procedure with acetonitrile was used for sample preparation. Thanks to the use of stable isotope-labeled internal standards for all analytes, internal standard-normalized matrix effects were in the range of 92-108%. The method was fully validated to cover large concentration ranges of 0.2-90ng/ml for haloperidol, 0.5-90ng/ml for flupentixol, 1-450ng/ml for levomepromazine, promazine and zuclopenthixol and 2-900ng/ml for cis-chlorprothixene and pipamperone. Trueness (89.1-114.8%), repeatability (1.8-9.9%), intermediate precision (1.9-16.3%) and accuracy profiles (<30%) were in accordance with the latest international recommendations. The method was successfully used in our laboratory for routine quantification of more than 500 patient plasma samples for therapeutic drug monitoring. To the best of our knowledge, this is the first UHPLC-MS/MS method for the quantification of the studied drugs with a sample preparation based on protein precipitation.

Jacobus de Vitriaco, Sermones vulgares seu ad omnes status.

Au f. 153, ex-libris lavé, du XIVe s. (lampe de Wood): "Iste liber est Hugoni de Villeni Sancti Ligari [...] quem emit ab exequo (?) defuncti domini Stephani de Susciaco presbiteri". Dans l'obituaire de la cathédrale de Paris, publié par A. Molinier (Obituaires de la province de Sens, I, Paris, 1902, 91-240), le décès de Stephanus de Susiaco [Etienne de Suizy], "presbiter cardinalis", est mentionné à la date du 11 décembre 1311 (p. 208). En-dessous, un second ex-libris du XIVe s. a été gratté: "Iste liber est [...] rectoris [...] Carnotensis dyocesis". Il est suivi par une mention d'achat partiellement lisible, du XIVe s.: "Vendidi [...] ante s. crucem text. sextio casus quosdam decretalium vendedi magister Stephanus de Lugello habuit [...] tamquam (?) de bonis iste [...] + Richardus ad bonum baculum tenetur presens I. et marg. emo [...], debet XXVII s. IIII d. par. medi augusti. Solvi V p. De quibus se [...] Anchi (?) Yvoni X sol. par. IIII d. par." Ce ms. a été acheté par Claude Joly, chantre de Notre-Dame de Paris, à Chaumont-en-Bassigny en 1655, comme l'indique la note de Claude Joly au contreplat sup.: "Cl. Joly M. oct. 1658. J'ay eu ce mss. a Chaumont en Bassigni en 1655". En-dessous de cette note figure l'ex-libris "A la bibliotheque de l'Eglise de Paris", précédé de la cote C18 (fin XVIIe s.-début XVIIIe s.). Notre-Dame.

A validated assay for measuring doxorubicin in biological fluids and tissues in an isolated lung perfusion model: matrix effect and heparin interference strongly influence doxorubicin measurements.

Doxorubicin is an antineoplasic agent active against sarcoma pulmonary metastasis, but its clinical use is hampered by its myelotoxicity and its cumulative cardiotoxicity, when administered systemically. This limitation may be circumvented using the isolated lung perfusion (ILP) approach, wherein a therapeutic agent is infused locoregionally after vascular isolation of the lung. The influence of the mode of infusion (anterograde (AG): through the pulmonary artery (PA); retrograde (RG): through the pulmonary vein (PV)) on doxorubicin pharmacokinetics and lung distribution was unknown. Therefore, a simple, rapid and sensitive high-performance liquid chromatography method has been developed to quantify doxorubicin in four different biological matrices (infusion effluent, serum, tissues with low or high levels of doxorubicin). The related compound daunorubicin was used as internal standard (I.S.). Following a single-step protein precipitation of 500 microl samples with 250 microl acetone and 50 microl zinc sulfate 70% aqueous solution, the obtained supernatant was evaporated to dryness at 60 degrees C for exactly 45 min under a stream of nitrogen and the solid residue was solubilized in 200 microl of purified water. A 100 microl-volume was subjected to HPLC analysis onto a Nucleosil 100-5 microm C18 AB column equipped with a guard column (Nucleosil 100-5 microm C(6)H(5) (phenyl) end-capped) using a gradient elution of acetonitrile and 1-heptanesulfonic acid 0.2% pH 4: 15/85 at 0 min-->50/50 at 20 min-->100/0 at 22 min-->15/85 at 24 min-->15/85 at 26 min, delivered at 1 ml/min. The analytes were detected by fluorescence detection with excitation and emission wavelength set at 480 and 550 nm, respectively. The calibration curves were linear over the range of 2-1000 ng/ml for effluent and plasma matrices, and 0.1 microg/g-750 microg/g for tissues matrices. The method is precise with inter-day and intra-day relative standard deviation within 0.5 and 6.7% and accurate with inter-day and intra-day deviations between -5.4 and +7.7%. The in vitro stability in all matrices and in processed samples has been studied at -80 degrees C for 1 month, and at 4 degrees C for 48 h, respectively. During initial studies, heparin used as anticoagulant was found to profoundly influence the measurements of doxorubicin in effluents collected from animals under ILP. Moreover, the strong matrix effect observed with tissues samples indicate that it is mandatory to prepare doxorubicin calibration standard samples in biological matrices which would reflect at best the composition of samples to be analyzed. This method was successfully applied in animal studies for the analysis of effluent, serum and tissue samples collected from pigs and rats undergoing ILP.

Simultaneous determination of antidementia drugs in human plasma: Procedure transfer from HPLC-MS to UPLC-MS/MS.

A previously developed high performance liquid chromatography mass spectrometry (HPLC-MS) procedure for the simultaneous determination of antidementia drugs, including donepezil, galantamine, memantine, rivastigmine and its metabolite NAP 226-90, was transferred to an ultra performance liquid chromatography system coupled to a tandem mass spectrometer (UPLC-MS/MS). The drugs and their internal standards ([(2)H(7)]-donepezil, [(13)C,(2)H(3)]-galantamine, [(13)C(2),(2)H(6)]-memantine, [(2)H(6)]-rivastigmine) were extracted from 250μL human plasma by protein precipitation with acetonitrile. Chromatographic separation was achieved on a reverse phase column (BEH C18 2.1mm×50mm; 1.7μm) with a gradient elution of an ammonium acetate buffer at pH 9.3 and acetonitrile at a flow rate of 0.4mL/min and an overall run time of 4.5min. The analytes were detected on a tandem quadrupole mass spectrometer operated in positive electrospray ionization mode, and quantification was performed using multiple reaction monitoring. The method was validated according to the recommendations of international guidelines over a calibration range of 1-300ng/mL for donepezil, galantamine and memantine, and 0.2-50ng/mL for rivastimgine and NAP 226-90. The trueness (86-108%), repeatability (0.8-8.3%), intermediate precision (2.3-10.9%) and selectivity of the method were found to be satisfactory. Matrix effects variability was inferior to 15% for the analytes and inferior to 5% after correction by internal standards. A method comparison was performed with patients' samples showing similar results between the HPLC-MS and UPLC-MS/MS procedures. Thus, this validated UPLC-MS/MS method allows to reduce the required amount of plasma, to use a simplified sample preparation, and to obtain a higher sensitivity and specificity with a much shortened run-time.

Assessment of human skin penetration of two irritant herbicides

Two common herbicides; isoproturon and bentazon, are strong skin irritants and cross the skin barrier easily. Assessment of percutaneous absorption of these substances is a very important step in the evaluation of any dermal or transdermal dose, especially among agricultural workers who frequently have dermal exposures during crop treatment. The aims of the study were to determine the permeation rate of human skin for both herbicides in vitro, and histologically evaluate skin damage due to irritation at different concentrations. Skin penetration was assessed using a dynamic flow-through in vitro penetration system and analysis were performed with ion trap LC-MS (acidified water: acetronitile, C18 column). Two concentrations of bentazon (75 and 150 μg/mL) and isoproturon (125 and 250 μg/mL) in saline solution were applied on excised human skin from several donors. Saline water was used as receptor fluid. Collection times were: 4, 8, and 24 hours. After the experiments, the skin was removed and examined by histopathology for apoptosis, acanthosis, acantholysis and epidermolysis. The skin permeation rate, J, was calculated from the slope of the cumulative amount permeated as a function of time. The lag time, tL, was assigned from the time-axis intercept of the extrapolation of this linearity. Our results showed that tL for bentazon and isoproturon for both concentrations tested were similar; 2, 1.5 hours, respectively. Bentazon had a lowerer J compared to isoproturon; 350, 600 ng/cm2/h, respectively. Some acanthosis was observed after 8 hours of exposure to either of the two substances. In conclusion, our in vitro experiments demonstrate that bentazon and isoproturon cross the skin barrier within 2 hours even at very low concentrations, and showed some signs of skin damage. Future tests involve concentrations found in commercial products.

Química e mineralogia de solos derivados de rochas do Grupo Bambuí no norte de Minas Gerais

Perfis de solos representativos do Distrito Agroindustrial do Jaíba, norte de Minas Gerais, foram descritos morfologicamente, tendo sido suas amostras coletadas e analisadas química, física e mineralogicamente, com o fim de obter informações que contribuam para sua melhor exploração agrícola. Embora provenientes, em sua quase totalidade, de calcário do grupo Bambuí, e com aparente homogeneidade fisiográfica (relevo plano e floresta caducifólia), os solos apresentaram grande diversidade nesses aspectos. Mineralogicamente, observaram-se a ilita e a caulinita como minerais comuns, esta última presente mesmo em Vertissolo e Rendzina, solos com expressiva quantidade de carbonatos livres. A presença de esmectita no Vertissolo, na Rendzina e no Cambissolo de argila de atividade alta indica que a escassez de chuva, a riqueza do material de origem e sua superficialidade em topografia plana dificultam a saída de sílica e bases do sistema, favorecendo a formação de esmectita. Tal mineralogia, associada à sazonalidade climática, parece responsável pelo fendilhamento expressivo desses solos no período seco. Os solos apresentam cores variadas: solos vermelhos e vermelho-amarelados, graças à presença de hematita e goethita, referem-se principalmente aos Latossolos situados em posições ligeiramente mais elevadas na paisagem, dispondo de melhor drenagem; amarelos e bruno-amarelados, normalmente situados em áreas mais deprimidas, que, aliados à superficialidade e massividade do material de origem, restringem a drenagem, favorecendo a gênese da goethita e levando à formação de concreções ferro-manganosas em quantidades expressivas; nestes ambientes, foram constatados Cambissolos de argila de atividade alta (Ta) e baixa (Tb), Vertissolos ou solos com características vérticas, também brunados, e Rendzina. A baixa relação Fe o/Fe d (ferro oxalato/ferro ditionito) revelou predomínio de óxidos mais cristalinos. Os solos eutróficos e epieutróficos (distróficos ou álicos), com baixos teores de Na e relevo dominantemente plano e suave-ondulado, confirmam a grande potencialidade agrícola da área, sobretudo sob irrigação. A diversidadade das características químicas, físicas e mineralógicas dos solos, entretanto, aponta variações de comportamento frente ao uso agrícola, indicando adequações diferenciadas de práticas de manejo.

Atributos micromorfológicos de solos do Projeto Jaíba, norte de Minas Gerais

Amostras indeformadas de horizontes representativos de solos do Projeto Jaíba, norte de Minas Gerais, e camadas compactadas e não compactadas de solos sob uso intensivo foram coletadas e analisadas micromorfologicamente, com vistas em obter maiores informações relativas ao seu grau de evolução e avaliar as alterações causadas nos solos pelo uso agrícola. Foram estudados quatro solos derivados de calcário (P1, P2, P3 e P4) e um originado a partir de sedimentos detríticos (P5), além das camadas com e sem indícios de compactação. A micromorfologia revelou que os solos apresentam características bastante distintas e variáveis, dependendo da classe e do material de origem. O Cambissolo originado de calcário tem como característica marcante o fluxo vertical de sílica e argila, sem, no entanto, caracterizar horizonte B textural, além de maior desenvolvimento de estrutura em blocos. O Cambissolo originado de sedimentos detríticos apresenta fluxo lateral de argila, presença marcante de cutãs de difusão de ferro e estrutura menos desenvolvida tendendo a granular. O Podzólico Vermelho-Escuro apresentou estrutura em blocos e presença de cutãs de deposição, muitos destes incorporados pela matriz, o que pode indicar transição para Latossolo. Os Latossolos apresentam-se com estrutura granular, mas esta é muito menos desenvolvida que a observada para os Latossolos gibbsíticos já analisados no País, o que pode indicar um menor grau de evolução destes solos. A atividade da fauna parece ser o principal agente responsável pelo desenvolvimento da microestrutura do Podzólico e dos Latossolos. Quanto à compactação, a micromorfologia relevou diferenças na organização do plasma e na forma dos poros, quando se compararam camadas compactadas com não compactadas. De maneira geral, o plasma das camadas compactadas é mais denso e os poros se apresentam alterados em razão do esforço físico impingido aos solos.

Liberação de nutrientes durante a decomposição de palha de aveia preta (Avena strigosa) com diferentes teores de silício

O Si absorvido pelas plantas é, em sua maior parte, depositado na parte externa da parede celular de folhas como uma camada de sílica amorfa (SiO2.nH2O) e poderia afetar a decomposição da palha no solo. Com o objetivo de avaliar o efeito da presença deste elemento no tecido vegetal sobre a decomposição da palha, foi desenvolvido um experimento. Nesse experimento, a parte aérea de plantas de aveia preta, cultivadas em solução nutritiva com e sem adição de Si, foi incubada em tubos de PVC com areia e solo. Aos 6, 14, 30, 66, 100 e 182 dias, foram realizadas percolações com água destilada e determinados os teores de Si, carbono orgânico solúvel, N mineral, Ca, Mg, Na e K. Os resultados dos teores dos elementos na água percolada em cada período foram convertidos em quantidade liberada por kg de substrato (solo ou areia) e acumulados no tempo para serem utilizados como índices da decomposição da palha. Em todos os parâmetros avaliados, não houve diferença significativa entre a palha c/Si e s/Si, exceto para o teor de Si e este somente quando a palha foi decomposta na areia. O silício absorvido pelas plantas de aveia preta, quando comparado com plantas cultivadas sem adição deste elemento, não alterou a liberação de carbono e nutrientes presentes na água de percolação durante o período de 182 dias da decomposição da palha.

Caracterização de concreções ferro-manganosas de solos de calcário no norte do estado de Minas Gerais

As concreções ferro-manganosas, variáveis quanto ao diâmetro e formato, são comuns em solos desenvolvidos de calcário no norte de Minas Gerais. Normalmente, tendem a aumentar de tamanho com a profundidade nos Cambissolos e Vertissolos e a permanecer pequenas nos Latossolos, onde são mais lisas (menos corroídas) e mais arredondadas (lembrando chumbinho de caça). Com o objetivo de estudá-las, foram coletadas concreções (C) nos horizontes B de Latossolos Vermelhos; B e BC de Cambissolo e C de Vertissolo, agrupadas de acordo com o diâmetro médio (C1-Φ = 0,18 cm; C2-Φ = 0,53 cm; C3-Φ = 0,90 cm; C4-Φ = 1,75 cm), sendo C1 as concreções dos Latossolos e C2, C3 e C4 separações das concreções do Cambissolo e do Vertissolo. Tais concreções, após trituradas, foram caracterizadas química (extração de Fe e Mn com oxalato e DCB; ataque sulfúrico e ataque triácido) e mineralogicamente (difração de raios-X). Também foram coletadas amostras indeformadas dos solos que apresentavam concreções, as quais foram impregnadas para análise micromorfológica. A caracterização química das concreções revelou o ferro, a sílica e o manganês como os principais constituintes. Houve correlação significativa e negativa entre o diâmetro das concreções e o teor de ferro (r = -0,88), o que concorda com a literatura, bem como maior acúmulo de ferro nas concreções de menor diâmetro. Também houve correlação positiva entre o diâmetro e o teor de sílica (r = 0,96), fato explicado pelos teores de sílica encontrados nos solos e horizontes onde as concreções ocorrem. Para o manganês nenhuma correlação foi observada, o que contradiz dados de literatura, que revelam normalmente aumento do teor de manganês com o diâmetro. Observou-se, ainda, nas concreções, alguns elementos traços (Ba, Co, Ni, Pb). A quantificação de elementos traços demonstrou elevadas concentrações de manganês, com valores médios 40 vezes maiores que os encontrados nos solos, valores elevados de bário (em média 20 vezes maiores que nos solos) e que tendem a acompanhar o manganês (r = 0,99), o que também foi verificado para o Co (r = 0,99), Ni (r = 0,94), Pb (r = 0,99). A difração de raios-X revelou a presença de goethita como único óxido de ferro presente. Também foi detectada a presença de quartzo, caulinita, lithiophorita e traços de minerais 2:1 (possivelmente interestratificados ilita/esmectita). A micromorfologia revelou a presença de concreções (com organização interna concêntrica) e de nódulos ferro-manganosos. Observando do centro para a periferia, as camadas concêntricas das concreções variaram do preto ao amarelo-avermelhado, evidenciando a contribuição do manganês e a possível transformação dos óxidos de ferro, talvez de hematita para goethita. Alguns fragmentos de concreções presentes nos solos encontravam-se recapeados por novos aportes de ferro, indicando que o processo de difusão e concentração do ferro continuava ativo.