Manganese and cobalt redox cycling in laterites; Biogeochemical and bioprocessing implications

This research was developed during the PhD studies of Agustín Solano Arguedas in the University of Manchester, United Kingdom. PhD scholarship was funded by the Ministerio de Ciencia, Tecnología y Telecomunicaciones (MICITT) of the Government of Costa Rica and the Universidad de Costa Rica (UCR). Agustín Solano Arguedas is a researcher at the Unidad de Recursos Forestales (Reforesta, Unit of Forest Resources) of the Instituto de Investigaciones en Ingeniería (INII, Engineering Research Institute), UCR.Cobalt is essential for the modern technology that underpins the decarbonisation of our economies, but its supply is limited leading to its designation as a critical metal. Cobalt biogeochemistry is poorly understood, yet knowledge of how biogeochemical cycling impacts cobalt behaviour could assist the development of new techniques to recover cobalt from ores, and so improve the security of supply. Laterites are an important source of cobalt, they are primarily processed for nickel using energy or chemical intensive processes, with cobalt recovered as a by-product. Metal-reducing conditions were stimulated in laterite sediment microcosms by the addition of simple and cheaply available organic substrates (acetate or glucose). At the end of the experiment the amount of easily recoverable cobalt (aqueous or extractable with acetic acid) increased from < 1% to up to 64%, which closely mirrored the behaviour of manganese, while only a small proportion of iron was transformed into an easily recoverable phase. Sequencing of the microbial community showed that the addition of organic substrates stimulated the growth of indigenous prokaryotes closely related to known manganese(IV)/iron(III)-reducers, particularly from the Clostridiales, and that fungi assigned to Penicillium, known to produce organic acids beneficial for leaching cobalt and nickel from laterites, were identified. Overall, the results indicate that the environmental behaviour of cobalt in laterites is likely to be controlled by manganese biogeochemical cycling by microorganisms. These results are compelling given that similar behaviour was observed in four laterites (Acoje, Çaldağ, Piauí and Shevchenko) from different continents. A new bioprocessing strategy is proposed whereby laterites are treated with an organic substrate to generate metal-reducing conditions, then rinsed with acetic acid to remove the cobalt. Not only are organic substrates environmentally-friendly and potentially sourced from waste carbon substrates, a minimal amount of iron oxides was mobilised and consequently less waste generated.Natural Environment Research Council/[CoG3 NE/M011518/1]/NERC/Reino UnidoDiamond Light Source/[SP16735]//Reino UnidoDiamond Light Source/[SP17313]//Reino UnidoOffice of Science User Facility/[DE-AC02-05CH11231]//Estados UnidosUCR::Vicerrectoría de Investigación::Unidades de Investigación::Ingeniería::Instituto Investigaciones en Ingeniería (INII

Comparison of gene transfection and cytotoxicity mechanisms of linear poly(amidoamine) and branched poly(ethyleneimine) polyplexes

Purpose: This study aimed to further explore the mechanisms behind the ability of certain linear polyamidoamines (PAAs) to transfect cells with minimal cytotoxicity. Methods: The transfection efficiency of DNA complexed with a PAA of a molecular weight over 10 kDa or 25 kDa branched polyethyleneimine (BPEI) was compared in A549 cells using a luciferase reporter gene assay. The impact of endo/lysosomal escape on transgene expression was investigated by transfecting cells in presence of bafilomycin A1 or chloroquine. Cytotoxicity caused by the vectors was evaluated by measuring cell metabolic activity, lactate dehydrogenase release, formation of reactive oxygen species and changes in mitochondrial membrane potential. Results: The luciferase activity was 3-fold lower after transfection with PAA polyplexes than with BPEI complexes at the optimal polymer to nucleotide ratio (RU:Nt). However, in contrast to BPEI vectors, PAA polyplexes caused negligible cytotoxic effects. The transfection efficiency of PAA polyplexes was significantly reduced in presence of bafilomycin A1 while chloroquine enhanced or decreased transgene expression depending on the RU:Nt. Conclusions: PAA polyplexes displayed a pH-dependent endo/lysosomal escape which was not associated with cytotoxic events, unlike observed with BPEI polyplexes. This is likely due to their greater interactions with biological membranes at acidic than neutral pH

High-performance liquid chromatographic determination of naproxen, ibuprofen and diclofenac in plasma and synovial fluid in man

High-performance liquid chromatographic assay procedures have been developed for naproxen, ibuprofen and diclofenac in human plasma and synovial fluid samples. A single liquid-liquid extraction procedure was used to isolate each compound from acidified biological matrix prior to the quantitative analysis. A Spherisorb ODS column (12.5 cm x 4.6 mm I.D.) was used for all the chromatography. Naproxen was eluted with a mobile phase of methanol-Sorensen's buffer at pH 7 (37:63, v/v). Ibuprofen and diclofenac were eluted using mobile phases of methanol-water at pH 3.3 (65:35, v/v and 63:37, v/v, respectively). Diphenylacetic acid was used as the internal standard for the assay of naproxen and flurbiprofen was used in the analysis of ibuprofen and diclofenac. Inter- and intra-day coefficients of variation were less than 7%. The assays were used in clinical studies of the three drugs in osteo- and rheumatoid arthritis patients

A global analysis of complexity–biodiversity relationships on marine artificial structures

Aim: Topographic complexity is widely accepted as a key driver of biodiversity, but at the patch-scale, complexity–biodiversity relationships may vary spatially and temporally according to the environmental stressors complexity mitigates, and the species richness and identity of potential colonists. Using a manipulative experiment, we assessed spatial variation in patch-scale effects of complexity on intertidal biodiversity. Location: 27 sites within 14 estuaries/bays distributed globally. Time period: 2015–2017. Major taxa studied: Functional groups of algae, sessile and mobile invertebrates. Methods: Concrete tiles of differing complexity (flat; 2.5-cm or 5-cm complex) were affixed at low–high intertidal elevation on coastal defence structures, and the richness and abundance of the colonizing taxa were quantified after 12 months. Results: The patch-scale effects of complexity varied spatially and among functional groups. Complexity had neutral to positive effects on total, invertebrate and algal taxa richness, and invertebrate abundances. However, effects on the abundance of algae ranged from positive to negative, depending on location and functional group. The tidal elevation at which tiles were placed accounted for some variation. The total and invertebrate richness were greater at low or mid than at high intertidal elevations. Latitude was also an important source of spatial variation, with the effects of complexity on total richness and mobile mollusc abundance greatest at lower latitudes, whilst the cover of sessile invertebrates and sessile molluscs responded most strongly to complexity at higher latitudes. Conclusions: After 12 months, patch-scale relationships between biodiversity and habitat complexity were not universally positive. Instead, the relationship varied among functional groups and according to local abiotic and biotic conditions. This result challenges the assumption that effects of complexity on biodiversity are universally positive. The variable effect of complexity has ramifications for community and applied ecology, including eco-engineering and restoration that seek to bolster biodiversity through the addition of complexity.</p

A global analysis of complexity–biodiversity relationships on marine artificial structures

Aim: Topographic complexity is widely accepted as a key driver of biodiversity, but at the patch-scale, complexity–biodiversity relationships may vary spatially and temporally according to the environmental stressors complexity mitigates, and the species richness and identity of potential colonists. Using a manipulative experiment, we assessed spatial variation in patch-scale effects of complexity on intertidal biodiversity. Location: 27 sites within 14 estuaries/bays distributed globally. Time period: 2015–2017. Major taxa studied: Functional groups of algae, sessile and mobile invertebrates. Methods: Concrete tiles of differing complexity (flat; 2.5-cm or 5-cm complex) were affixed at low–high intertidal elevation on coastal defence structures, and the richness and abundance of the colonizing taxa were quantified after 12 months. Results: The patch-scale effects of complexity varied spatially and among functional groups. Complexity had neutral to positive effects on total, invertebrate and algal taxa richness, and invertebrate abundances. However, effects on the abundance of algae ranged from positive to negative, depending on location and functional group. The tidal elevation at which tiles were placed accounted for some variation. The total and invertebrate richness were greater at low or mid than at high intertidal elevations. Latitude was also an important source of spatial variation, with the effects of complexity on total richness and mobile mollusc abundance greatest at lower latitudes, whilst the cover of sessile invertebrates and sessile molluscs responded most strongly to complexity at higher latitudes. Conclusions: After 12 months, patch-scale relationships between biodiversity and habitat complexity were not universally positive. Instead, the relationship varied among functional groups and according to local abiotic and biotic conditions. This result challenges the assumption that effects of complexity on biodiversity are universally positive. The variable effect of complexity has ramifications for community and applied ecology, including eco-engineering and restoration that seek to bolster biodiversity through the addition of complexity