Patterning total mercury distribution in coastal podzolic soils from an Atlantic area: influence of pedogenetic processes and soil components

Soils are the main Hg reservoir in the terrestrial ecosystems where it is deposited via wet or dry deposition and litterfall. Once on the soil surface, different biogeochemical routes will determine the fate of Hg and the role of terrestrial ecosystems as a Hg source or sink. The specific chemical and physical characteristics of Podzols and podzolic soils contribute to the accumulation of Hg in their illuvial horizons, avoiding its leaching to groundwater. The geographical location, state of pedogenesis, soil age, abundance of carrier phases and physical properties can affect the presence and distribution of Hg in soils. Therefore, understand and relate these factors with the behavior of Hg in Podzols and podzolic soils is key to define the role of this type of soil in the terrestrial Hg cycle. In this work, ten podzolic soil profiles were collected in an Atlantic coastal forest area of Portugal and analyzed for the main physico-chemical properties and Hg content to assess the influence of the intensity of podzolization in the Hg depth distribution. Three different patterns of Hg distribution in the studied Podzols, depending on the predominance of atmospheric deposition or the intensity of podzolization, have been defined. The pattern I showed the maximum Hg contents in the surface A horizons (12.9–23.5 μg kg 1), pattern II exhibited the highest peaks in the subsurface illuvial horizons (2.3–17.3 μg kg 1) and pattern III presented an even distribution of Hg through the soil profile. We found that dissolved organic matter (DOM) is the main carrier of Hg in the A and E horizons, whereas metal(Al, Fe)-humus complexes and/or oxyhydroxides contribute to immobilizing Hg in the illuvial horizons (Bh, Bs and Bhs). The principal component regression (PCR) analysis predicted satisfactorily the Hg distribution through soil organic matter and Al and Fe oxyhydroxides. The Hg immobilized in the subsurface layers of Podzols is retained in the long term, avoiding its migration to other components of terrestrial ecosystems where it could cause serious environmental damage such as groundwater and superficial watersinfo:eu-repo/semantics/publishedVersio

Cr(VI) sorption/desorption on untreated and mussel-shell-treated soil materials: fractionation and effects of pH and chromium concentration

We used batch-type experiments to study Cr(VI) sorption/desorption on granitic material, forest soil, pyritic material, mussel shell, and on forest soil and granitic material amended with 12 t ha−1 (1.2 kg m −2) shell, considering the effects of varying Cr(VI) concentration and pH. Sequential extractions were carried out to fractionate adsorbed Cr(VI) and to determine the stability of Cr(VI) retention. The pyritic material had the highest Cr(VI) retention capacity, whereas the granitic material showed the lowest retention potential. When high Cr concentrations were added, some saturation of the adsorbent surfaces became apparent, but Cr release remained low. The highest Cr retention was achieved at a very acid pH value, with release progressively increasing as a function of increasing pH. The amendment with 12 t ha−1 mussel shell did not cause marked changes in Cr(VI) retention. Sorption data were satisfactory adjusted to the Freundlich model. Regarding Cr(VI) fractionation, the soluble fraction (weakly bound) was dominant in mussel shell and in the unamended and amended granitic material, whereas more stable fractions dominated in the pyritic material (residual fraction) and in the forest soil (oxidizable fraction). In conclusion, the pyritic material presented the highest Cr(VI) retention capacity, while the retention was low and weak on the granitic material; mussel shell was not characterized by a marked Cr(VI) retention potential, and it did not cause remarkable increase in Cr(VI) retention when used to amend the granitic material or the forest soil.This study was funded by the Ministerio de Economía y Competitividad (Government of Spain), grant numbers CGL2012-36805-C02-01-02S

The role of afforestation species as a driver of Hg accumulation in organic horizons of forest soils from a Mediterranean mountain area in SW Europe

Forest areas are a primary sink of atmospheric mercury (Hg) within terrestrial ecosystems, whereas forest vegetation plays a key role in atmospheric Hg transfer to soil horizons. This study assessed variations in total Hg contents (HgT) and accumulation (HgRes) in the soil organic horizons of a forest area in NE Portugal, where post-wildfire afforestation led to the substitution of the native deciduous species (Quercus pyrenaica) by fast-growing coniferous species (Pseudotsuga menziesii and Pinus nigra). The study also evaluated, for each species, the links between Hg contents and other biophilic elements of soil organic matter (C, N, S) present in organic subhorizons (OL, OF, OH). Mean HgT in the organic horizons of the different tree species follow the sequence: P. nigra (88 μg kg−1) < Q. pyrenaica (101 μg kg−1) < P. menziesii (141 μg kg−1). The highest HgRes for the entire organic horizon was found under P. menziesii (471 μg m−2), followed by P. nigra (253 μg m−2) and Q. pyrenaica (189 μg m−2). Among the organic subhorizons, values of HgT and HgRes follow the sequence OL < OF < OH, which is consistent with the degree of organic matter humification. Indeed, HgT and HgRes correlated significantly with the C/N and C/S ratios for all species and organic subhorizons, suggesting that the quality of organic matter may influence strongly the Hg fate in these forest soils. Soils from P. menziesii plots have shown an HgRes 2.5 times higher than in plots dominated by the native Q. pyrenaica. Hg accumulation in the organic horizons, promoted in the coniferous species, may increase the risk of Hg mobilization due to wildfires and forest management practices. Therefore, forest management plans should select cautiously the tree species for afforestation in order to minimize adverse environmental effects caused by changes in the biogeochemical cycle of contaminants such as Hg.M. Méndez-López acknowledges the predoctoral grant FPU of Ministerio de Educación y Formación Profesional (FPU17/05484). It is also recognized the financial support of the Consellería de Cultura, Educación e Universidade (Xunta de Galicia) through the contract ED431C 2021/46-GRC granted to the research group BV1 of the University of Vigo and the research project ED431F2018/06-EXCELENCIA.info:eu-repo/semantics/publishedVersio

Sulfadiazine, sulfamethazine and sulfachloropyridazine removal using three different porous materials: Pine bark, “oak ash” and mussel shell

This work focuses on studying the efficacy of three different by-products to adsorb three antibiotics (sulfadiazine, SDZ; sulfamethazine, SMT; sulfachloropyridazine, SCP). These antibiotics can be considered pollutants of the environment when they reach water, as well as in cases where they are spread on soils through irrigation or contained in sewage sludge or livestock manure. In this study, batch-type adsorption/desorption experiments were performed for each of the three sulfonamides, adding 7 different concentrations of the antibiotics, going from 1 to 50 μmol L−1, and with contact time of 24 h. The results indicate that pine bark is the most efficient bioadsorbent among those studied, as it adsorbs up to 95% of the antibiotics added, while desorption is always less than 11%. However, for “oak ash” and mussel shell the adsorption is always lower than 45 and 15%, respectively, and desorption is high, reaching up to 49% from “oak ash” and up to 81% from mussel shell. Adsorption data showed good fitting to the Linear and Freundlich models, with R2 values between 0.98 and 1.00 in both cases. Kd and KF adsorption parameters showed similar values for the same sorbent materials but were much higher for pine bark than for the other two bioadsorbents. The Freundlich's n parameter showed values in the range 0.81–1.28. The highest KF values (and therefore the highest adsorption capacities) were obtained for the antibiotic SCP in pine bark. Pine bark showed the highest capacity to adsorb each of the antibiotics, increasing as a function of the concentration added. When the concentration of sulfonamide added was 50 μM, the amounts adsorbed were 780 μmol kg−1 for SDZ, 890 μmol kg−1 for SMT, and 870 μmol kg−1 for SCP. “Oak ash” and mussel shell have low adsorption capacity for all three sulfonamides, showing values always lower than 150 μmol kg−1 (oak ash) and 20 μmol kg−1 (mussel shell) when a concentration of 50 μmol L−1 of antibiotic is added. The results of this study could aid to make an appropriate management of the by-products studied, in order to facilitate their valorization and recycling in the treatment of environmental compartments polluted with sulfonamide antibiotics.Agencia Estatal de Investigación | Ref. RTI2018-099574-B-C21Agencia Estatal de Investigación | Ref. RTI2018-099574-B-C2

Influencia del tipo de vegetación en la cantidad de Hg acumulado en horizontes orgânicos de suelos forestales del NE de Portugal

El papel de los suelos forestales como reservorio de Hg es clave en su ciclo biogeoquímico en los ecosistemas terrestres, función que puede verse influenciada por el tipo de especie forestal en base a la diferente capacidad de estas para capturar el Hg atmosférico y de transferirlo hacia los horizontes superficiales mediante la caída de material senescente. El principal objetivo de este estudio es evaluar el efecto del tipo de especie forestal en la presencia y acumulación (reservorio) de Hg en los horizontes orgánicos de suelos forestales. En el NE de Portugal se seleccionaron nueve parcelas forestales, tres dominadas por Pseudotsugamenziesii (PM), otras tres por Pinusnigra (PN) y tres más por Quercuspyrenaica (QP). En todas ellas se tomaron muestras de los horizontes orgánicos (Oi, Oe y Oa) en 5 localizaciones diferentes, analizando los niveles de Hg total (HgT) en cada una de las muestras (n= 134). Los niveles medios de HgT en los suelos de las parcelas de PM fueron 112, 170 y 142 ng g‐1 en los subhorizontes Oi, Oe y Oa, respectivamente. Estos valores fueron significativamente mayores que sus equivalentes en los suelos de PN (65, 92 y 108 ng g‐1 en Oi, Oe y Oa) y en los de QP (75, 106 y 122 ng g‐1 en Oi, Oe y Oa), mientras que no hubo diferencias entre los subhorizontes O de PN y QP. El HgT acumulado en los horizontes orgánicos (reservorio) fue también significativamente mayor en las parcelas de PM cuyos valores (83, 162 y 226 μg m‐2 para subhorizontes Oi, Oe y Oa, respectivamente) son el doble del que presentan las parcelas de PN (47, 74 y 108 μg m‐2 para Oi, Oe y Oa) y de QP (45, 40 y 105 μg m‐2 para Oi, Oe y Oa). Estos resultados indican que el tipo de especie ejerce una notable influencia en la presencia y acumulación de HgT en las capas más superficiales de los suelos forestales, especialmente cuando se trata de coníferas.info:eu-repo/semantics/publishedVersio

The clinical and molecular cardiometabolic fingerprint of an exploratory psoriatic arthritis cohort is associated with the disease activity and differentially modulated by methotrexate and apremilast

Objectives: (1) To evaluate clinical and molecular cardiovascular disease (CVD) signs and their relationship with psoriatic arthritis (PsA) features and (2) to identify a clinical patient profile susceptible to benefit from methotrexate (MTX) and/or apremilast regarding CVD risk. Methods: This cross-sectional study included 100 patients with PsA and 100 age-matched healthy donors. In addition, an exploratory cohort of 45 biologically naïve patients treated for 6 months with apremilast, MTX or combined therapy according to routine clinical practice was recruited. Extensive clinical and metabolic profiles were obtained. Ninety-nine surrogate CVD-related molecules were analysed in plasma and peripheral blood mononuclear cells (PBMCs). Hard cluster analysis was performed to identify the clinical and molecular phenotypes. Mechanistic studies were performed on adipocytes. Results: Cardiometabolic comorbidities were associated with disease activity and long-term inflammatory status. Thirty-five CVD-related proteins were altered in the plasma and PBMCs of PsA patients and were associated with the key clinical features of the disease. Plasma levels of some of the CVD-related molecules might distinguish insulin-resistant patients (MMP-3, CD163, FABP-4), high disease activity (GAL-3 and FABP-4) and poor therapy outcomes (CD-163, LTBR and CNTN-1). Hard cluster analysis identified two phenotypes of patients according to the rates of cardiometabolic comorbidities with distinctive clinical and molecular responses to each treatment. Conclusions: (1) Novel CVD-related proteins associated with clinical features could be emerging therapeutic targets in the context of PsA and (2) the pleiotropic action of apremilast could make it an excellent choice for the management of PsA patients with high CVD risk, targeting metabolic alterations and CVD-related molecules

Assessing the effectiveness of a three-stage on-farm biobed in treating pesticide contaminated wastewater

Agricultural point source pesticide pollution arising from contaminated machinery washings and accidental spillages pose a significant threat to river water and groundwater quality. In this study, we assess the effectiveness of a three-stage on-farm biobed for treating pesticide contaminated waste water from a large (20 km2) commercial arable estate. The facility consisted of an enclosed machinery wash-down unit (stage 1), a 49 m2 lined compost-straw-topsoil biobed (stage 2), and a 200 m2 drainage field with a trickle irrigation system (stage 3). Pesticide concentrations were analysed in water samples collected fortnightly between November 2013 and November 2015 from the biobed input and output sumps and from 20 porous pots buried at 45 cm and 90 cm depth within the drainage field. The results revealed that the biobed removed 68–98% of individual pesticides within the contaminated washings, with mean total pesticide concentrations reducing by 91.6% between the biobed input and output sumps. Drainage field irrigation removed a further 68–99% of individual pesticides, with total mean pesticide concentrations reducing by 98.4% and 97.2% in the 45 cm and 90 cm depth porous pots, respectively. The average total pesticide concentration at 45 cm depth in the drainage field (57 µg L-1) was 760 times lower than the mean concentration recorded in the input sump (43,334 µg L-1). There was no evidence of seasonality in the efficiency of biobed pesticide removal, nor was there evidence of a decline in removal efficiency over the two-year monitoring period. However, higher mean total pesticide concentrations at 90 cm (102 µg L-1) relative to 45 cm (57 µg L-1) depth indicated an accumulation of pesticide residues deeper within the soil profile. Overall, the results presented here demonstrate that a three-stage biobed can successfully reduce pesticide pollution risk from contaminated machinery washings on a commercial farm