Copper accumulation and fractionation in vineyard soils from temperate humid zone (NW Iberian Peninsula)

The occurrence of total Cu and Cu fractions (exchangeable Cu, Cu bound to organic matter, Cu bound to amorphous inorganic materials, Cu bound to crystalline Fe and Al oxides and residual Cu) was studied in 170 surface layers of soils from seven vineyard regions located in the NW Iberian Peninsula (Rías Baixas, Ribeira Sacra, Ribeiro, Monterrei, Valdeorras, O Bierzo and Vinhos Verdes). The data showed that long-term application of Cu-based fungicides has led to increased concentrations, mainly in superficial vineyard soil layers. Thus, 64% of the samples showed total Cu levels higher than 100 mg kg 1, threshold for soil contamination. Total Cu content in Ribeiro (248 ± 130 mg kg 1) and Ribeira Sacra (259 ± 118 mg kg 1) soils were significantly higher than those observed for the rest of the vineyard regions (169 ± 90, 139 ± 122, 115 ± 42, 103 ± 42 and 100 ± 48 mg kg 1 in Valdeorras, Rías Baixas, O Bierzo, Vinhos Verdes and Monterrei, respectively). Cu distribution among various soil fractions also differed between winegrowing regions; however, in general, Cu in these vineyard soils is present mainly in less mobile fractions (average values were 48 ± 12% for Cu bound to soil organic matter; 15 ± 9% for Cu associated to amorphous inorganic materials; 12 ± 9% for Cu bound to crystalline Fe and Al oxides and 23 ± 12% for residual Cu), whereas exchangeable Cu constituted approximately 3 ± 3% of total Cu. All soil samples were separated in three well differentiated groups according to their physical, chemical and Cu fractionation data (Ribeiro, Ribeira Sacra and Monterrei samples; O Bierzo, Valdeorras and Monterrei samples; Rías Baixas and Vinhos Verdes samples), being soil type, climate and fungicide application as the most determinant factors for soil quality.Xunta de Galici

Copper distribution and acid‐base mobilization in vineyard soils and sediments from Galicia (NW Spain)

In northern Spain and elsewhere in the world, many vineyards are located on steep slopes and are susceptible to accelerated soil erosion. Contaminants, notably Cu, originating from repeated application of copper‐based fungicides to the vines to prevent mildew, are transported and stored in the sediments deposited close to valley bottoms. In this study, the contents and distribution of Cu in 17 soil samples and 21 sediment samples collected from vineyard stands were determined. In addition, the effect of pH on Cu release from vineyard soils and sediments was quantified. The total Cu content (Cu T) in the soils varied between 96 and 583 mg kg−1, and was between 1.2 and 5.6 times greater in sediment samples. The mean concentration of potentially bioavailable Cu (Cu EDTA) in the sediments was 199 mg kg−1 (46% of Cu T), and was 80 mg kg −1 (36% of Cu T) in the soils. Copper bound to soil organic matter (Cu OM) was the dominant fraction in the soils (on average, 53% of the Cu T), while in sediment samples Cu OM values varied between 37 and 712 mg kg−1 and were significantly greater (P < 0.01) than in the soils. Copper associated with non‐crystalline inorganic components (Cu IA) was the second most important fraction in the sediments, in which it was 3.4 times greater than in the soils. Release of Cu due to changes in the pH followed a U‐shaped pattern in soils and sediments. The release of Cu increased when the pH decreased below 5.5 due to the increased solubility of the metal at this pH. When the pH increased above 7.5, Cu and organic matter were released simultaneously.Ministerio de Educación y Ciencia | Ref. AGL2006-04231/AG

SentiNet: Detecting Physical Attacks Against Deep Learning Systems

SentiNet is a novel detection framework for physical attacks on neural networks, a class of attacks that constrains an adversarial region to a visible portion of an image. Physical attacks have been shown to be robust and flexible techniques suited for deployment in real-world scenarios. Unlike most other adversarial detection works, SentiNet does not require training a model or preknowledge of an attack prior to detection. This attack-agnostic approach is appealing due to the large number of possible mechanisms and vectors of attack an attack-specific defense would have to consider. By leveraging the neural network's susceptibility to attacks and by using techniques from model interpretability and object detection as detection mechanisms, SentiNet turns a weakness of a model into a strength. We demonstrate the effectiveness of SentiNet on three different attacks - i.e., adversarial examples, data poisoning attacks, and trojaned networks - that have large variations in deployment mechanisms, and show that our defense is able to achieve very competitive performance metrics for all three threats, even against strong adaptive adversaries with full knowledge of SentiNet.Comment: 15 page

Carbon mineralization in acidic soils amended with an organo-mineral bentonite waste

Bentonite based organic-mineral wastes contains high concentrations of organic matter and plant nutrients and hence presents a high potential as a soil amendment. However, it also can have high salinity and high copper concentrations that may cause negative effects on microorganisms when the soil is amended with this type of wastes. In this work, the effect of soil amendment with a bentonite based winery waste on soil carbon mineralization was studied in acidic vineyard soils as an indicator of soil quality. The carbon mineralization in the waste is significantly lower and slower than that in the studied vineyard soils despite its significantly higher amount of organic carbon. However, when the bentonite winery waste was added to the soils, the carbon mineralization showed positive priming effects (increased between 78 and 337%). Therefore, reductions in the carbon mineralization, and hence changes on short-term organic matter turnover are not expected after bentonite waste amendment in acid soils.Xunta de Galicia | Ref. (FEADER2009-22) CO-106-0

Copper retention kinetics in acid soils

Retention and release kinetics of Cu on four acid Typic haplumbrepts developed on two different types of parent rock material (granite and amphibolite) were studied with a stirred-flow chamber (SFC) method. The granitic soils were lower in organic material and lower in Fe and Al oxides than the soils formed in amphibolite. The kinetic parameters were assessed in four consecutive Cu retention–release cycles by alternately applying pulses of solutions with and without Cu. Granite soils showed lower total Cu retention (7–12 mmol kg−1) than amphibolite soils (16–21 mmol kg−1) after one single pulse application of 0.0787 mmol Cu L−1 at pH 5.5, which may be due to differences in their organic and oxides compositions. The amount of Cu retained diminished to 40 to 25% in the third retention cycle relative to the first, suggesting that the soils’ Cu retention depends on the previous metal loading. Conversely, the released Cu was approximately 20% of that retained in the first cycle, but the amounts released were similar for all cycles and all soils. The results obtained were fitted using a first-order equation for both retention and release of Cu. In the first cycle, first order rate coefficients of retention ranged from 0.084 to 0.56 min−1, and increased by about a factor of two in the next cycle. Release rate coefficients were more than 10 times lower than those of retention, and less dependent on the previous metal loading. The process of retention and release of Cu was found to be hysteretic, which suggest that the desorption mechanism or path is not an exact opposite of the adsorption mechanism or path.Ministerio de Educación y Ciencia | Ref. AGL2006-04231/AG

Mercury mobilization in shrubland after a prescribed fire in NE Portugal: insight on soil organic matter composition and different aggregate size

Soils constitute the major reservoir of mercury (Hg) in terrestrial ecosystems, whose stability may be threatened by wildfires. This research attempts to look at the effect of prescribed fire on the presence of Hg in a shrubland ecosystem from NE Portugal, delving into its relationship with soil aggregate size and the molecular composition of soil organic matter (SOM). During the prescribed fire, on average 347 mg Hg ha 1 were lost from the burnt aboveground biomass of shrubs and 263 mg Hg ha 1 from the combustion of the soil organic horizon. Overall, Hg concentration and pools in the mineral soil did not show significant changes due to burning, which highlights their role as long-term Hg reservoirs. The higher Hg concentrations found in smaller aggregates (<0.2 mm) compared to coarser ones (0.5–2 mm) are favored by the higher degree of organic matter decomposition (low C/ N ratio), rather than by greater total organic C contents. The Hg-enriched finest fraction of soil (<0.2 mm) could be more prone to be mobilized by erosion, whose potential arrival to water bodies increases the environmental concern for the Hg present in fire-affected soils. The SOM quality (molecular composition) and the main organic families, analyzed by Fourier-transform infrared spectroscopy in combination with multivariate statisticalThis work was supported by the Interreg V-A Spain-Portugal program (POCTEP) 2014–2020 (Project 0701_TERRAMATER_1_E) funded by the European Regional Development Fund (FEDER), the EROFIRE project (PCIF/RPG/0079/2018) funded by FCT, Portugal and the InMerForEcos project (PID 2021-125114OB-I00) funded by Ministerio de Ciencia e Innovaciónn and Agencia Estatal de Investigaciónn (MCIN/ AEI) and FEDER. M. Méndez-López was supported by the predoctoral grant FPU (FPU17/05484) funded by the Ministerio de Educaciónn y Formación Profesional. N.T. Jiménez-Morillo was supported by a “Ramón y Cajal” contract (RYC2021-031253-I) funded by MCIN/AEI/10 .13039/501100011033 and the European Union “NextGenerationEU”/ PRTR”. The financial support of the Consellería de Cultura, Educación e Universidade (Xunta de Galicia) through the contract ED431C2021/46- GRC granted to the research group BV1 of the University of Vigo is also recognized. Open-access funding for this research has been provided by the University of Vigo/CISUG.info:eu-repo/semantics/publishedVersio

Soil erosion in mountain shrub areas: effect of prescribed fire

Atualmente, um dos maiores problemas ambientais ao nível do globo é a perda de solo por erosão hídrica. O agente erosivo pode provocar perdas significativas de nutrientes e matéria orgânica, principalmente quando a superfície do solo suporta um reduzido coberto vegetal. Em Portugal, o fogo controlado é uma prática comumente utilizada no controlo da disponibilidade de combustível e consequente redução do risco de incêndio. Contudo, esta prática remove em grande parte a cobertura vegetal, deixando o solo mais exposto aos processos erosivos. Neste sentido, o presente trabalho tem como objetivo avaliar o efeito do fogo controlado na erosão hídrica em áreas de matos do Parque Natural de Montesinho, NE Portugal. Após o fogo, foram instaladas 6 parcelas de erosão de 4 m2 cada (4 × 1 m), para avaliação da perda de solo e do escoamento superficial na área queimada. Os resultados englobam 8 meses de ensaio (março a dezembro de 2021), e as colheitas foram realizadas por cada evento de precipitação, perfazendo um total de 6 avaliações. O volume de água de escoamento e a perda de solo (massa de sedimentos) foram obtidos através de cálculos que englobaram o escoamento, os sedimentos transportados para o interior dos reservatórios de colheita do escoamento e os sedimentos depositados na parte frontal das parcelas de erosão (colocação de um dispositivo que permite a recolha dos sedimentos transportados). A quantidade média de perda de solo foi de 15,4 g m-2, o escoamento superficial médio foi de 1,4 mm, traduzindo-se num coeficiente de escoamento de 4,2%. Para avaliação das perdas de C e N, os sedimentos foram separados em 4 classes de tamanho (2mm) e analisadas em laboratórios as concentrações de C e N. A baixa precipitação total, durante o período de ensaio, ocasionou baixos valores de escoamento e, portanto, baixos valores de perda de solo, de C e de NCurrently, one of the biggest environmental problems at the global level is the soil loss by water erosion. The erosive agent can cause significant losses of nutrients and organic matter, especially when the soil surface supports a reduced vegetation cover. In Portugal, prescribed fire is a commonly used practice to control the fuel availability and consequently reduce the wildfires risk. However, this practice removes the vegetation cover, leaving the soil more exposed to erosive processes. In this sense, the present work aims to evaluate the effect of prescribed fire on water erosion in shrub areas of the Montesinho Natural Park, NE Portugal. After the fire, 6 erosion plots of 4 m2 each (4 × 1 m) were installed to assess soil loss and runoff in the burned area. The results encompass 8 months (March to December 2021), and samples were collected for each rainfall event, making a total of 6 evaluations. The runoff and soil loss (sediment mass) were obtained through calculations that encompassed the runoff, the sediments transported into the runoff collection reservoirs and the sediments deposited on the front of the erosion plots (placement of a device that allows the collection of transported sediments). The average of soil loss was 15.4 g m-2, the average of runoff was 1.4 mm, corresponding to a runoff coefficient of 4.2%. To evaluate C and N losses, the sediments were separated into 4 size classes (2mm) and analyzed in laboratory the C and N concentrations. The low total precipitation, during the test period, caused low runoff values and, therefore, low losses of soil, C and N.TERRAMATER- Innovative preventive recovery measures in burnt areas, 0701_TERRAMATER_ 1_E, co-funded by FEDER through Interreg V-A España-Portugal (POCTEP) 2014–2022. Fundação para a Ciência e a Tecnologia (FCT, Portugal) e fundos nacionais FCT/MCTES (PIDDAC) pelo apoio financeiro ao CIMO (UIDB/00690/2020 e UIDP/00690/2020) e SusTEC (LA/P/0007/2020).info:eu-repo/semantics/publishedVersio

Chromium VI and Fluoride Competitive Adsorption on Different Soils and By-Products

Chromium (as Cr(VI)) and fluoride (F−) are frequently found in effluents from different industrial activities. In cases where these effluents reach soil, it can play an important role in retaining those pollutants. Similarly, different byproducts could act as bio-adsorbents to directly treat polluted waters or to enhance the purging potential of soil. In this work, we used batch-type experiments to study competitive Cr(VI) and F− adsorption in two different soils and several kinds of byproducts. Both soils, as well as mussel shell, oak ash, and hemp waste showed higher adsorption for F−, while pyritic material, pine bark, and sawdust had a higher affinity for Cr(VI). Considering the binary competitive system, a clear competition between both elements in anionic form is shown, with decreases in adsorption of up to 90% for Cr(VI), and of up to 30% for F−. Adsorption results showed better fitting to Freundlich’s than to Langmuir’s model. None of the individual soils or byproducts were able to adsorbing high percentages of both pollutants simultaneously, but it could be highly improved by adding pine bark to increase Cr(VI) adsorption in soils, thus drastically reducing the risks of pollution and deleterious effects on the environment and on public healthThis research was funded by the SPANISH MINISTRY OF ECONOMY AND COMPETITIVENESS by means of the research projects CGL2012-36805-C02-01 and CGL2012-36805-C02-02. It was also partially financed by the European Regional Development Fund (FEDER in Spain)S

Metais pesados em solos de pastagem da A Pastoriza (NO Espanha) tratados com chorume de vaca e adubos NPK

In Galicia (NW Spain), pasturelands cover a broad extension and are mainly used to feed cattle. Farms are managed in an intensive manner, using cattle slurry and inorganic fertilizers to increase pasture production, but also increasing risks of heavy metal pollution. In this work we studied the influence of fertilization practices on total concentrations and in-depth distribution of heavy metals and related elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn) in two forest soils (SN1, SN2) and five pastureland soils (P1-P5) fertilized with cattle slurry and NPK, in a broadly exploded farmland area (A Pastoriza, Lugo). Soils SN2 and P4 were developed over slate, whereas soils SN1, P1, P2, P3 and P5 evolved on Candana quartzite. Forest soils presented acid pH (4.58-4.68), high Al saturation (75-90%), and low available P concentration (4.78-11.96 mg kg-1), whereas those parameters exhibited better scores in the pastureland soils, due to previous amendment and fertilization practices, thus giving pH 5.17-7.02, Al saturation 0.58-59.24%, and available P 5.24-42.07 mg kg-1. Regarding heavy metals, soil depth did not affect significantly to total concentrations, contrary to that happening with parent material, with higher As, Cu, Fe, and Ni concentrations found in soils over slate (possibly due to the presence of pyritic materials). In most cases, heavy metal total concentrations were lower than that considered as reference background levels for soils developed over each of the parent materials, and were always lower than that considered phyto-toxic. In this study, natural soils usually presented heavy metal total contents similar or even higher than that of the fertilized soils (unless Zn in the P4 pastureland), thus indicating that the spread doses of fertilizers did not influence significantly their concentration levels.En Galicia las praderas ocupan una gran extensión, siendo utilizadas principalmente para la alimentación del ganado vacuno destinado tanto a la producción de leche como de carne. Las granjas se manejan de manera intensiva, utilizando fertilizantes inorgánicos y purín de vacuno para aumentar la producción de pastos. Esta práctica puede aumentar el contenido de metales pesados en el suelo. En este trabajo se estudian las concentraciones totales y la distribución en profundidad de metales pesados y elementos afines (As, Cd, Cr, Cu, Mn, Ni, Pb y Zn) en dos suelos forestales (SN1, SN2) y en cinco praderas (P1-P5) fertilizadas con purín de vacuno y NPK en una zona con una gran vocación ganadera (A Pastoriza, Lugo). Se pretende conocer el grado de influencia de la fertilización sobre los niveles de estos elementos. Los suelos elegidos se desarrollaron a partir de pizarras (SN2, P4) y de cuarcitas de la Serie de Cándana (SN1, P1, P2, P3, P5). Los suelos forestales presentaron pH ácido (4,58-4,68), elevada saturación del complejo de cambio por Al (75-90%) y baja concentración de P disponible (4,78-11,96 mg kg-1); estos parámetros mejoran en los suelos de pradera como consecuencia de las enmiendas y fertilizantes aplicados, presentando un pH entre 5,17 y 7,02, una saturación de Al que varía entre 0,58-59,24% y P disponible entre 5,24 y 42,07 mg kg-1. En relación con los metales pesados, la profundidad de la muestra no afecta de modo significativo a su concentración total, pero sí el material de partida, presentando concentraciones más elevadas de Fe, As, Cu y Ni los suelos desarrollados sobre pizarras, posiblemente debido a la presencia de materiales piríticos. En la mayoría de los casos, los metales pesados estudiados presentan concentraciones totales inferiores a las establecidas como genéricas para suelos desarrollados sobre los respectivos materiales geológicos, y siempre son menores que los límites considerados fitotóxicos. La fertilización aplicada no parece tener una influencia significativa sobre los contenidos totales de estos elementos, con la excepción del Zn en la pradera P4, ya que los suelos naturales en muchos casos presentan valores similares e incluso superiores a los obtenidos en las parcelas fertilizadas.As pastagens ocupam uma grande área na região da Galicia (NO Espanha) destnando-se sobretudo à alimentação de bovinos para produção de leite e carne. As explorações são geridas de forma intensiva, aplicando-se adubos minerais e chorumes com o objetivo de aumentar a produção de pastos. Contudo, esta prática pode aumentar o teor de metais pesados no solo. Neste trabalho, a concentração total e a distribuição em profundidade de metais pesados e elementos associados (As, Cd, Cr, Cu, Mn, Ni, Pb e Zn) foram estudados em dois solos florestais (SN1, SN2) em cinco talhões (P1-P5) adubados com NPK e chorume de bovino, numa área com uma grande vocação para pecuária (A Pastoriza, Lugo). Teve-se por objetivo principal determinar o grau de influência da fertilização nos teores destes elementos. Os solos selecionados foram desenvolvidos a partir de ardósias (SN2, P4) e quartzitos da Série de Candana (SN1, P1, P2, P3, P5). Os solos florestais apresentavam pH ácido (4,58-4,68), alta saturação de Al (75-90%) no complexo de troca de e baixa concentração de P disponível (4,78-11,96 mg kg-1); estes parâmetros melhoram em solos de pastagem, como resultado da calagem e fertilizantes aplicados, apresentando um pH entre 5,17 e 7,02; saturação por Al variando de 0,58 a 59,24% e P disponível entre 5,24 e 42,07 mg kg-1. Em relação aos metais pesados, a profundidade da amostra não afetou significativamente a sua concentração total, contrariamente ao que se verificou com o material parental, que apresentou as concentrações mais elevadas de Fe, As, Cu e Ni nos solos desenvolvidos a partir de ardósias possivelmente devido à presença de materiais piríticos. Na maioria dos casos, os metais pesados estudados apresentaram concentrações totais inferiores aos valores geralmente considerados como referência para solos desenvolvidos a partir dos respetivos materiais parentais, sendo sempre inferiores aos valores limite considerados fitotóxicos. Neste estudo, os solos naturais apresentaram valores de metais pesados semelhantes ou mesmo superiores aos dos solos fertilizados (exceto para o Zn na pastagem P4), o que indica que as doses aplicadas de fertilizantes não influenciaram de forma significativa os seus níveis de concentração.This work was funded by the Spanish Ministerio de Economía y Competitividad (Grant Reference: CGL2012-36805-C02-01)S