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)

Secondary metabolite biosynthetic diversity in the fungal family Hypoxylaceae and Xylaria hypoxylon.

To date little is known about the genetic background that drives the production and diversification of secondary metabolites in the Hypoxylaceae. With the recent availability of high-quality genome sequences for 13 representative species and one relative (Xylaria hypoxylon) we attempted to survey the diversity of biosynthetic pathways in these organisms to investigate their true potential as secondary metabolite producers. Manual search strategies based on the accumulated knowledge on biosynthesis in fungi enabled us to identify 783 biosynthetic pathways across 14 studied species, the majority of which were arranged in biosynthetic gene clusters (BGC). The similarity of BGCs was analysed with the BiG-SCAPE engine which organised the BGCs into 375 gene cluster families (GCF). Only ten GCFs were conserved across all of these fungi indicating that speciation is accompanied by changes in secondary metabolism. From the known compounds produced by the family members some can be directly correlated with identified BGCs which is highlighted herein by the azaphilone, dihydroxynaphthalene, tropolone, cytochalasan, terrequinone, terphenyl and brasilane pathways giving insights into the evolution and diversification of those compound classes. Vice versa, products of various BGCs can be predicted through homology analysis with known pathways from other fungi as shown for the identified ergot alkaloid, trigazaphilone, curvupallide, viridicatumtoxin and swainsonine BGCs. However, the majority of BGCs had no obvious links to known products from the Hypoxylaceae or other well-studied biosynthetic pathways from fungi. These findings highlight that the number of known compounds strongly underrepresents the biosynthetic potential in these fungi and that a tremendous number of unidentified secondary metabolites is still hidden. Moreover, with increasing numbers of genomes for further Hypoxylaceae species becoming available, the likelihood of revealing new biosynthetic pathways that encode new, potentially useful compounds will significantly improve. Reaching a better understanding of the biology of these producers, and further development of genetic methods for their manipulation, will be crucial to access their treasures.

Housing and accessibility after the COVID-19 pandemic: Rebuilding for resilience, equity and sustainable mobility.

A more sustainable post COVID-19 world requires urban transport policies aiming for resilience, social equity and decarbonisation. Instead of just focusing on the transport sector, the authors propose an integrated approach to housing and mobility. This approach acknowledges the challenges posed by inadequate housing and dependence on motorised transport during the COVID-19 crisis. In contrast, adequate housing and cycling became paramount resources while confronting the pandemic. Using Santiago de Chile as a case study, this research examines how different relocation scenarios for its current housing deficit cannot only affect the ability to implement stay-at-home measures, but also the potential of cycling as a relevant commuting alternative. The current location of the families suffering this deficit is compared to three scenarios: compact, pericentral and extended. In light of the learnings from the COVID-19 crisis, a housing-cycling policy becomes a tool for resilience; equity is achieved by enforcing the right to housing, by increasing job opportunities among the poor, and by reducing the dependence on expensive motorised transport; decarbonisation is achieved by promoting active transportation and reducing the dependence on motorisation.

Litterfall Hg deposition to an oak forest soil from southwestern Europe.

Litterfall constitutes one of the main vectors for mercury (Hg) transfer to forested ecosystems, so we studied the deposition of Hg through senescent vegetation (oak leaves, twigs and miscellaneous) in a deciduous forest plot of Southwest Europe dominated by Quercus robur in 2015 and 2016. Total Hg concentrations increased in the following order: bole wood (1.4 µg kg-1) < bark (8.3 µg kg-1) < twigs (12.2 µg kg-1) < miscellaneous (36.0 µg kg-1) < oak leaves (39.3 µg kg-1) < mineral soil (42.4 µg kg-1) < Oi horizons (48.7 µg kg-1) < Oe + Oa horizons (71.6 µg kg-1). Mercury accumulation rates in oak leaves during the growing season were 0.15-0.18 µg kg-1 day-1. Mercury deposition fluxes were 26 and 21 µg m-2 yr-1 for 2015 and 2016, respectively, with oak leaves being the fraction that contributed the most. Mercury determination in litterfall sorted biomass fractions lead to a more accurate estimation of the total annual Hg deposition fluxes through litterfall. Higher Hg content was obtained for organic horizons (average of 60.2 µg kg-1) than for mineral soil (mean of 42.4 µg kg-1), but the soil Hg pool was higher in the latter. The results confirmed the necessity of taking into account the Hg pool in the deeper mineral soil layers as they accumulate substantial quantities of Hg associated to organic C and Al compounds, preventing its mobilization to other compartments of the terrestrial ecosystems.

Experimental data and model prediction of tetracycline adsorption and desorption in agricultural soils.

In this work, tetracycline (TC) adsorption and desorption were studied, and the soil properties that most influenced the process were identified. Batch experiments were carried out on 63 crop soil samples, which showed a wide range of values in their physicochemical characteristics. Adsorption curves fit well to the Freundlich equation, with KF values varying between 901 and 9202 Ln µmol1-n kg-1. Kd values ranged between 53 and 6899 L kg-1 for an initial concentration (Co) of 400 µM, whereas the adsorption capacity (qa) ranged from 8541 to 14,852 µmol kg-1. TC retention on soils was high, with adsorption values always higher than 58%, and desorption values lower than 9%. Bivariate correlations and multiple linear regressions were performed to identify those soil variables having a greater influence on TC adsorption and desorption. The results indicate that organic carbon, clay, exchangeable aluminum, available phosphorus, effective cation exchange capacity content, and pH are the main characteristics affecting TC adsorption and desorption. The models, developed by means of multiple linear regression, gave satisfactory and robust predictions for TC adsorption and desorption, using easily determinable soil characteristics as input.

Pedotransfer functions to estimate the adsorption and desorption of sulfadiazine in agricultural soils.

Batch-type experiments were used to study adsorption-desorption of sulfadiazine in 50 crop soils exposed to antibiotic pollution due to the spreading of animal manure or slurry. Adsorption and desorption curves were linear, and were satisfactorily described using the linear and Freundlich equations. The Freundlich adsorption constant (KF(ad)) showed low values (between 0.4 and 9.0 L1/n µmol1-1/n kg-1), which were similar to those of the adsorption constant for the linear model (Kd(ad), between 0.3 and 12.0 L kg-1). Furthermore, the desorption constant for the linear model (Kd(des)) showed higher values than those of Kd(ad), ranging between 1.6 and 29.3 L kg-1, while the values of the Freundlich desorption constant (KF(des)) ranged from 0.10 to 36.8 L1/n µmol1-1/n kg-1. The percentages of adsorption were very variable, ranging from 10 to 87%. The soil characteristics that most influenced adsorption-desorption were those related to soil organic matter (organic carbon and nitrogen contents), as well as the effective cation exchange capacity, and pH. In addition, statistically robust pedotransfer functions were obtained, allowing prediction of adsorption-desorption behavior for sulfadiazine from readily determinable soil parameters, such as pH or organic carbon content.

Copper and zinc in rhizospheric soil of wild plants growing in long-term acid vineyard soils. Insights on availability and metal remediation.

Total and available Cu and Zn levels were assessed in plant biomass, as well as in two rhizosphere fractions (tightly adhering rhizosphere (TAR), and loosely adhering rhizosphere (LAR)), in wild plants species from vineyard soils. Both TAR and LAR fractions were enriched in total Cu and Zn (1.7 and 1.6 times, respectively), and in available Cu and Zn (2.2 and 19.5 times, respectively), with the former being significantly higher for TAR than for LAR fractions. Mean values for total Cu accumulation in root and aerial biomass of the studied wild plants were 84 and 66 mg kg-1, respectively, being 57 and 79 mg kg-1 for Zn. No correlations were found among metal contents in plant biomass and available Cu and Zn concentrations in the rhizosphere fractions. Translocation factor (TF) values for Zn (range 1.0-3.5) indicate preferential accumulation in the aerial biomass in all the studied wild plants. On the contrary, TF for Cu shows a greater variability, depending on plant species, and ranging from 0.2 to 5.9. Regarding bioaccumulation factor (BAF), ranges were 0.03-0.27 and 0.13-0.58, for Cu and Zn, respectively. Results suggest that D. sanguinalis, P. hieracioides, S. viridis, and T. barbata could be useful for Cu remediation in the studied soils, by means of phytostabilization processes.

Degradation of sulfadiazine, sulfachloropyridazine and sulfamethazine in aqueous media.

Antibiotics discharged to the environment constitute a main concern for which different treatment alternatives are being studied, some of them based on antibiotics removal or inactivation using by-products with adsorbent capacity, or which can act as catalyst for photo-degradation. But a preliminary step is to determine the general characteristics and magnitude of the degradation process effectively acting on antibiotics. A specific case is that of sulfonamides (SAs), one of the antibiotic groups most widely used in veterinary medicine, and which are considered the most mobile antibiotics, causing that they are frequently detected in both surface- and ground-waters, facilitating their entry in the food chain and causing public health hazards. In this work we investigated abiotic and biotic degradation of three sulfonamides (sulfadiazine -SDZ-, sulfachloropyridazine -SCP-, and sulfamethazine -SMT-) in aqueous media. The results indicated that, in filtered milliQ water and under simulated sunlight, the degradation sequence was: SCP > SDZ ≈ SMT. Furthermore, the rate of degradation clearly increased with the raise of pH: at pH 4.0, half-lives were 1.2, 70.5 and 84.4 h for SCP, SDZ and SMT, respectively, while at pH 7.2 they were 2.3, 9.4 and 13.2 h for SCP, SMT and SDZ. The addition of a culture medium hardly caused any change in degradation rates as compared to experiments performed in milliQ water at the same pH value (7.2), suggesting that in this case sulfonamides degradation rate was not affected by the presence of some chemical elements and compounds, such as sodium, chloride and phosphate. However, the addition of bacterial suspensions extracted from a soil and from poultry manure increased the rate of degradation of these antibiotics. This increase in degradation cannot be attributed to biodegradation, since there was no degradation in the dark during the time of the experiment (72 h). This indicates that photo-degradation constitutes the main removal mechanism for SAs in aqueous media, a mechanism that in this case was favored by humic acids supplied with the extracts from soil and manure. The overall results could contribute to the understanding of the environmental fate of the three sulfonamides studied, aiding to program actions that could favor their inactivation, which is especially relevant since its dissemination can involve serious environmental and public health risks.

Biotic and abiotic dissipation of tetracyclines using simulated sunlight and in the dark.

Veterinary antibiotics reaching soils and water bodies are considered emerging pollutants deserving special attention. In this work, dissipation of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) is investigated. Dissipation experiments in filtered water, using simulated sunlight, resulted in the following degradation sequence: TC < OTC ≈ CTC, with half-life values of 229, 101 and 104 min, respectively; however, no dissipation took place in the dark. Dissipation of the three tetracyclines in culture medium and with simulated sunlight was much higher, giving the sequence TC ≈ OTC < CTC, with half-lives of 9, 10 and 7 min, respectively; in the dark, TC and OTC did not suffer dissipation, but it was around 28% for CTC at the end of the experiment (480 min). The variable explaining a higher dissipation in culture medium and with light was pH, as this parameter caused changes in the distribution of species of tetracyclines, affecting degradation. Adding bacterial suspensions extracted from soil and poultry manure increased dissipation, giving the sequence: TC ≈ OTC < CTC, which is attributed to the presence of humic acids, which adsorb these antibiotics. These results could facilitate understanding the fate of antibiotics reaching environmental compartments and causing public health hazards.

Retention and transport of mecoprop on acid sandy-loam soils.

Interaction with soil components is one of the key processes governing the fate of agrochemicals in the environment. In this work, we studied the adsorption / desorption and transport of mecoprop (methylchlorophenoxypropionic acid or MCPP) in four acid sandy-loam soils with different organic matter contents. Kinetics of adsorption and adsorption/desorption at equilibrium were studied in batch experiments, whereas transport was studied in laboratory columns. Adsorption and desorption were found to be linear or nearly-linear. The kinetics of mecoprop adsorption were relatively fast in all cases (less than 24h). Adsorption and desorption were adequately described by the linear and Freundlich models, with KF values that ranged from 0.7 to 8.8Ln µmol1-nkg-1 and KD values from 0.3 to 3.6Lkg-1. The results of the transport experiments showed that the retention of mecoprop by soil was very low (less than 6.2%). The retention of mecoprop by the soils in all experiments increased with organic matter content. Overall, it was observed that mecoprop was weakly adsorbed by the soils, what would result in a high risk of leaching of this compound in the environment.

Netrin-1 and multiple sclerosis: a new biomarker for neuroinflammation?

BACKGROUND AND PURPOSE: Netrin-1, an axon guidance protein, reduces serum levels of pro-inflammatory mediators and stabilizes the blood-brain barrier limiting the entrance of immune cells into the central nervous system. The aim was to investigate its presence in the experimental autoimmune encephalomyelitis (EAE) model and in multiple sclerosis (MS) patients with and without clinical activity. METHODS: Netrin-1 levels were evaluated in EAE mouse tissues. Afterwards, serum netrin-1 was cross-sectionally quantified in 90 patients with different MS phenotypes and 30 control subjects. An additional group of 10 relapsing-remitting MS (RRMS) patients was longitudinally evaluated throughout a relapse (RRMSr) with an interval of 60 days. Tumour necrosis factor α (TNFα), a reference inflammatory cytokine, and netrin-1 were quantified by enzyme-linked immunosorbent assay. RESULTS: Experimental autoimmune encephalomyelitis mice showed significantly lower netrin-1 levels and higher TNFα amounts in sera, spinal cord and cerebella than healthy control mice. MS patients showed significantly lower serum netrin-1 levels than controls (511.62 ± 209.30 and 748.32 ± 103.24 pg/ml, respectively; P ≤ 0.005). The lowest protein levels were found in RRMSr, remaining significantly lower throughout the relapse. TNFα serum concentrations were higher in MS patients compared to controls, and negatively correlated with netrin-1 levels (r = -0.3734, P ≤ 0.0001). CONCLUSIONS: Netrin-1 decreased in EAE and in MS patients, mainly during relapse, suggesting an anti-inflammatory role of netrin-1. Further research should be performed in a larger cohort of patients to validate netrin-1 as a biomarker of MS inflammatory activity.

Removal of anionic pollutants by pine bark is influenced by the mechanism of retention.

The use of organic biosorbents for anion removal from water has been less studied than for cationic compounds. In this work, the removal capacity of pine bark for potential anionic pollutants (fluoride, phosphate, arsenate and dichromate) was assessed in column experiments, designed to study the process of transport. The results showed that pine bark has a very low retention capacity for phosphate, arsenate or fluoride, and in turn, very high for dichromate, with retention values close to 100% and less than 2% desorption of the adsorbed dichromate. The large differences observed between anions suggest that differences in the retention mechanism of each anion exist. In the case of phosphate and arsenate, electrostatic interactions with the mostly negatively charged functional groups of the pine bark determine the low retention capacity. Dichromate retention might proceed through reduction of chromium (VI) to chromium (III), what improves the efficiency of the removal.

Study of metal transport through pine bark for reutilization as a biosorbent.

The potential utilization of pine bark as a biosorbent for the treatment of metal-contaminated soils and waters has been evaluated in transport experiments using laboratory columns. Solutions containing the metals Cu, Pb, Zn, Ni or Cd, each one individually and at three different concentrations (2.5, 10 and 25 mM) were tested. Pine bark affected metal transport and the breakthrough curves, producing a reduction of their concentrations in the solution and a clear retardation with respect to an inert tracer. At metal concentrations equal to 2.5 mM, 100% of the assayed elements were removed from the solution in the pine bark column. At the 10 mM metal concentration, the percentage of metals retained fell to 38-67% of the amount added, whereas at the 25 mM metal concentration, only 16-43% was retained. In all cases, the highest retention capacity corresponded to Pb, and the lowest to Zn, whereas Cu, Cd and Ni produced intermediate comparable results. The analysis of the pine bark within the columns after the transport experiment showed that the metals entering the column adsorb progressively until a saturation concentration is reached in the whole column, and only then they can be released at significant concentrations. This saturation concentration was approximately 70 mmol kg(-1) for Cd, Ni and Zn, 100 mmol kg(-1) for Cu, and 125 mmol kg(-1) for Pb. Overall, our experiments have shown the high effectiveness of pine bark to retain the assayed metals in stable forms of low mobility.

Pine bark as bio-adsorbent for Cd, Cu, Ni, Pb and Zn: batch-type and stirred flow chamber experiments.

The objective of this work was to determine the retention of five metals on pine bark using stirred flow and batch-type experiments. Resulting from batch-type kinetic experiments, adsorption was rapid, with no significant differences for the various contact times. Adsorption was between 98 and 99% for Pb(2+), 83-84% for Cu(2+), 78-84% for Cd(2+), 77-83% for Zn(2+), and 70-75% for Ni(2+), and it was faster for low concentrations, with Pb suffering the highest retention, followed by Cu, Cd, Ni and Zn. The fitting to the Freundlich and Langmuir models was satisfactory. Desorption increased in parallel to the added concentrations, with Pb always showing the lowest levels. Stirred flow chamber experiments showed strong hysteresis for Pb and Cu, sorption being mostly irreversible. The differences affecting the studied heavy metals are mainly due to different affinity for the adsorption sites. Pine bark can be used to effectively remove Pb and Cu from polluted environments.

Heavy metal retention in copper mine soil treated with mussel shells: batch and column experiments.

Batch and column experiments are used to study the effects of ground mussel shell amendment on the retention of heavy metals in acidic mine soil. The soil pH increases proportionally with the mussel shell concentration employed. Mussel shell amendment increases Cu, Cd, Ni and Zn retention in mine soil when compared with unamended soil. In fact, Cu retention was 6480µmolkg(-1) (43% of the total added) when the maximum metal concentration (1570µM) was added to the unamended soil, whereas retention reached 15,039µmolkg(-1) (99.9% of the total Cu added) when soil was amended with 24gkg(-1) mussel shell; in the case of Cd, adsorption increases from 3257µmolkg(-1) (15% of the total added) for the unamended soil, to 13,200µmolkg(-1) (87% of the total added) for the shell-amended soil; Ni retention increased from 3767µmolkg(-1) (25% of the total added) corresponding to unamended soil, to 11,854µmolkg(-1) (77% of the total added) for the shell-amended soil; and finally, Zn retention increased from 4684µmolkg(-1) (31% of the total added), for unamended soil, to 14,952µmolkg(-1) (98% of the total added) for shell-amended soil. The results of the constant flow transport experiments show that the addition of the 24gkg(-1) mussel shells can retain Cu, Cd, Ni and Zn within the first few centimetres of the column length, indicating the usefulness of ground mussel shells to drastically decrease the mobility and availability of these pollutants and to facilitate soil remediation.

Decreased acid suppression therapy overuse after education and medication reconciliation.

BACKGROUND: Acid suppression therapy (AST) is commonly overprescribed in hospitalised patients. This indiscriminate use increases cost and drug-related side effects. Minimal data is available on interventions aimed at reducing the burden of overprescription. The aim of our study was to evaluate the impact of education and medication reconciliation forms use on admission as well as discharge, on AST overuse in hospitalised patients. METHODS: A retrospective chart review of randomly selected patients admitted to the general medicine service at University of Florida Health Science Center/Jacksonville was performed prior to and after the introduction of interventions (education/medication reconciliation) aimed at reducing AST overuse. The percentage of patients started on inappropriate AST, the admitting diagnosis, indications for starting AST and discharge on these medications was compared in the pre and postintervention groups. RESULTS: Acid suppression therapy use declined from 70% (279/400) in the preintervention period to 37% (100/270) postintervention (p < 0.001). There was a reduction in inappropriate prescriptions from 51% (204/400) pre to 22% (60/270) postintervention (p < 0.02). Stress ulcer prophylaxis in low-risk patients or the concomitant use of ulcerogenic drugs continued to motivate inappropriate AST therapy in most patients. Postintervention, only 20% (12/60) of patients were discharged on unneeded AST compared with 69% (140/204) in the preintervention group (p < 0.001). CONCLUSION: Interventions consisting of education and use of medication reconciliation forms decreased inappropriate prescription of AST on admission and discharge. This can significantly decrease cost to the healthcare system and the risk of drug interactions.

Copper fractionation and release from soils devoted to different crops.

We studied copper release as a function of pH in eight samples of acid soils under vine and maize crops containing variable concentrations of total copper (Cu(t)) from 55 to 112 mg kg(-1). Although both types of soil had similar Cu(t) values, the origin of the copper was essentially anthropogenic in the vineyard soils and natural (as result of weathering of parent material) in those under maize. The disparate origin of the metal resulted in marked differences in its fractions, particularly as regards organically bound copper, which was much more abundant in the vineyard soils. This had a strong effect on copper release as a function of pH, which was one order of magnitude greater in the vineyard soils than in those under maize.

Quaternary herbicides retention by the amendment of acid soils with a bentonite-based waste from wineries.

The agronomic utility of a solid waste, waste bentonite (WB), from wine companies was assessed. In this sense, the natural characteristics of the waste were measured, followed by the monitoring of its effects on the adsorption/desorption behaviour of three quaternary herbicides in acid soils after the addition of increasing levels of waste. This was done with the intention of studying the effect of the added organic matter on their adsorption. The high content in C (294 g kg(-1)), N (28 g kg(-1)), P (584 mg kg(-1)) and K (108 g kg(-1)) of WB turned it into an appropriate amendment to increase soil fertility, solving at the same time its disposal. WB also reduced the potential Cu phytotoxicity due to a change in Cu distribution towards less soluble fractions. The adsorption of the herbicides paraquat, diquat and difenzoquat by acid soils amended with different ratios of WB was measured. In all cases, Langmuir equation was fitted to the data. Paraquat (PQ) and diquat (DQ) were adsorbed and retained more strongly than difenzoquat (DFQ) in the acid soil studied. However, the lowest retention of DFQ in an acid soil can be increased by amendment with organic matter through a solid waste from wineries, and it is enough for duplicate retention a dosage rate of 10t/ha. Anyway, detritivores ecology can still be affected. Detritivores are the organisms that consume organic material, and in doing so contribute to decomposition and the recycling of nutrients. The term can also be applied to certain bottom-feeders in wet environments, which play a crucial role in benthic ecosystems, forming essential food chains and participating in the nitrogen cycle.

Influence of organic matter removal on competitive and noncompetitive adsorption of copper and zinc in acid soils.

We studied competitive and noncompetitive adsorption of copper and zinc in four acid soils, and compared the behavior of the two metals in untreated samples and samples treated with hydrogen peroxide to remove organic matter in the soil. Copper exhibited stronger competitive adsorption than zinc in the untreated samples. However, removal of organic matter reduced copper adsorption to a greater extent than zinc adsorption, the two metals exhibiting a more similar adsorption pattern than the untreated samples. The presence of copper dramatically reduced zinc competitive adsorption in untreated samples; on the other hand, that of zinc only resulted in slightly reduced competitive adsorption of copper. The hydrogen peroxide treatment decreased competitive adsorption in both metals; however, copper continued to be more efficient than zinc in competing for binding sites on adsorbing surfaces. Desorption of Cu occurred much less readily than desorption of Zn and hysteresis is apparent especially for Cu.