Biodeterioration and Chemical Corrosion of Concrete in the Marine Environment: Too Complex for Prediction.

Concrete is the most utilized construction material worldwide. In the marine environment, it is subject to chemical degradation through reactions with chloride (the most important ion), and sulfate and magnesium ions in seawater, and to biodeterioration resulting from biological (initially microbiological) activities, principally acid production. These two types of corrosions are reviewed and the failure of attempts to predict the degree of deterioration resulting from each is noted. Chemical (abiotic) corrosion is greatest in the splash zone of coastal constructions, while phenomenological evidence suggests that biodeterioration is greatest in tidal zones. There have been no comparative experiments to determine the rates and types of microbial biofilm formation in these zones. Both chemical and microbiological concrete deteriorations are complex and have not been successfully modeled. The interaction between abiotic corrosion and biofilm formation is considered. EPS can maintain surface hydration, potentially reducing abiotic corrosion. The early marine biofilm contains relatively specific bacterial colonizers, including cyanobacteria and proteobacteria; these change over time, producing a generic concrete biofilm, but the adhesion of microorganisms to concrete in the oceans has been little investigated. The colonization of artificial reefs is briefly discussed. Concrete appears to be a relatively prescriptive substrate, with modifications necessary to increase colonization for the required goal of increasing biological diversity.

Comparing the concentrations of heavy metals on two bivalve species in Santos Bay, Brazil: Subsidies to understanding the assimilation dynamic of bivalve contaminants.

Contaminant substances consist of chemical elements that present the potential to adversely impact the ecology of the environment, thus representing a threat to local fauna and flora. In this context, heavy metals are critical agents that, depending on the nature and level, are potentially toxic to living organisms. In order to evaluate the bioaccumulation of heavy metals in the Santos estuary and to determine the potential influence of salinity gradient on the heavy metal bioconcentration, the present study measured the concentrations of As, Cd, Pb, Cu, Cr, Fe, Ni, and Zn in two bivalve species (Crassostrea rhizophorae and Perna Perna) sampled at different sites of Santos Bay, in the southeastern region of Brazil. Throughout the study, the "sentinel species" used were effective in bioaccumulating contaminants. In oysters, based on the Brazilian legislation, critical limits were exceeded for As, Zn, Cu, and Cr. In the case of mussels, on the other hand, only for As, Zn, and Cr, the critical limits were overcome. In the present study, obtained data suggested salinity as a determinant parameter in As incorporation processes of bivalve mollusks. PRACTITIONER POINTS: The present study presents important results for the development of environmental management policies in estuarine environments. The present study points out differences between different organisms as biomonitors, providing subsidies for the decision of an effective biomonitoring program. The present study discusses values of contaminants as a danger to public health in Santos Bay, which can be extrapolated to other similar environments around the world.

Paint fragments as polluting microplastics: A brief review.

Paint particles are part of the increasingly important microplastics (MPs) pollution of our oceans. They contain polyurethanes, polyesters, polyacrylates, polystyrenes, alkyls and epoxies. In spite of their prevalence, paint fragments are often excluded from MP audits. This review, citing 127 references, discusses detection, characteristics, sources and ecological effects of paint fragments in our oceans, as well as the abundance of paint fragments in MP samples around the world and their colonization by marine microorganisms, which differs from that of non-paint MPs. Paint MPs arise from shipping and boating activities, road markings and external surfaces of buildings. Many paint fragments come from antifouling paints used on commercial vessels and leisure boats; these may be regarded as particular pollutants, not only containing but also leaching heavy metals and biocides. Some effects of antifouling paint particles on aquatic biota are caused by these toxins. Paint particles are an understudied portion of marine MP pollution.

Nanoplastics in aquatic systems - are they more hazardous than microplastics?

The fragmentation of plastic materials into nanoparticles of less than 1000 nm (secondary nanoplastics) and their possible accumulation in the environment is a recent matter of concern. There are still no suitable standard methods for determining the concentrations and chemical makeup of these particles in aquatic systems and the fate and effect of nanoplastics in the aquatic environment has been little explored, although there has been research using engineered nanoparticles as models. In this review, we give a summary of the (mainly laboratory-based) studies on the influences of nanoplastics. We aim to provide an updated overview of this emerging topic, reviewing the literature mainly from 2018 onwards and considering the effects of nanoplastics on ecosystems, their uptake and transport of polluting molecules, and the challenges that are faced by workers in this area. The review includes 119 references.

16S rRNA gene profiling of planktonic and biofilm microbial populations in the Gulf of Guinea using Illumina NGS.

16S rRNA gene profiling using a pipeline involving the Greengenes database revealed that bacterial populations in innermost (proximal to the steel surface) and outer regions of biofilms on carbon steel exposed 3 m below the surface at an offshore site in the Gulf of Guinea differed from one another and from seawater. There was a preponderance of gammaproteobacterial sequences, representing organisms known for hydrocarbon degradation. Total DNA from the innermost layer was 1500 times that recovered from the outermost. Stramenopiles (diatom) sequences were prevalent in the former. Rhodobacteriaceae, key biofilm formers, comprised 14.9% and 4.22% OTUs of inner and outer layers, respectively. Photosynthetic anaerobic sulfur oxidizer sequences were also prominent in the biofilms. Analysis of data using a different pipeline with Silva111 allowed detection of 0.3-0.4% SRB in the biofilms. The high abundance of aerobic micro-algal sequences in inner biofilm suggests they are initial colonizers of carbon steel surfaces in a marine environment. This is the first time that the microbial population of the strongly attached inner layer of the biofilm on steel has been differentiated from the outer, readily removed layer. The accepted scraping removal method is obviously inadequate and the resulting microbial analysis does not offer complete information on the biofilm community structure.

Microbial colonization affects the efficiency of photovoltaic panels in a tropical environment.

Sub-aerial biofilm (SAB) development on solar panels was studied in São Paulo. After 6, 12 and 18 months' exposure, photovoltaic panels were covered by increasing proportions of organic matter (42%, 53% and 58%, respectively). Fungi were an important component of these biofilms; very few phototrophs were found. Major microorganisms detected were melanised meristematic ascomycetes and pigmented bacterial genera Arthrobacter and Tetracoccus. While diverse algae, cyanobacteria and bacteria were identified in biofilms at 6 and 12 months, diversity at a later stage was reduced to that typical for SAB: the only fungal group detected in 18 month biofilm was the meristematic Dothideomycetes and the only phototrophs Ulothrix and Chlorella. Photovoltaic modules showed significant power reductions after 6, 12 (both 7%) and 18 (11%) months. The lack of difference in power reduction between 6 and 12 months reflects the dual nature of soiling, which can result from the deposition of particulates as well as from SAB fouling. Although 12-month old SAB demonstrated an almost 10-fold increase in fungal colonization and a higher organic content, the larger non-microbial particles (above 10 µm), which were important for efficiency reduction of lightly-biofilmed panels, were removed by high rainfall just before the 12-month sampling.

A conductive polymer based electronic nose for early detection of Penicillium digitatum in post-harvest oranges.

We describe the construction of an electronic nose, comprising four chemiresistive sensors formed by the deposition of thin conductive polymer films onto interdigitated electrodes, attached to a personal computer via a data acquisition board. This e-nose was used to detect biodeterioration of oranges colonized by Penicillium digitatum. Significant responses were obtained after only 24 h of incubation i.e. at an early stage of biodeterioration, enabling remedial measures to be taken in storage facilities and efficiently distinguishing between good and poor quality fruits. The instrument has a very low analysis time of 40 s.

Succession of fungi colonizing porous and compact limestone exposed to subtropical environments.

Little is known about the dynamics of succession of fungi on limestone exposed in subtropical environments. In this study, the colonization of experimental blocks of compact and porous limestone by a fungal community derived from natural biofilms occurring on Structure X from the archaeological site of Becán (México), was studied using a cultivation-dependent approach after short-term (9 m) exposure in order to provide a preliminary insight of the colonization process under seminatural conditions. Microbial growth seen as the change of colour of stone surfaces to black/dark green was more abundant on the porous limestone. There was a fairly clear difference in microbial colonization between the onset of the experiment and the 6th month for both limestone types, but no significant increase in the colonization of coupons occurred between months 6 and 9. This could be related to the low rainfall expected for this period, corresponding to the dry season. A total of 977 isolates were obtained. From these, 138 sterile fungi were unidentified, 380 could only be assigned to the order Sphaeropsidales; the remaining isolates (459) were grouped into 27 genera and 99 different species. Nearly all detected fungal species belonged to the Ascomycota (90 %). Rare taxa (species represented by one to three isolates) included the recently described genus Elasticomyces, several species of genera Hyalodendron, Monodyctis, Papulospora, Curvularia, and Septoria. Other taxa were Minimedusa and Gliomastix luzulae, which have not been previously described for stone environments. Abundant fungi included several species of the common genera Cladosporium, Alternaria, and Taeniolella typical for a range of habitats. Succession of populations was observed for certain taxa, this shift in the composition of fungal communities was more evident in porous limestone. After 6 m of exposure, species of the genera Scolecobasidium, Hyalodendron, and Taeniolella were predominant, while after 9 m, the predominant species belonged to the genera Curvularia and Alternaria, particularly on porous stone. These results suggest that Curvularia and Alternaria replaced other fungi, due to a higher tolerance towards low levels of available water during the dry season. Higher levels of water within the porous stone, keep longer periods of microbial activity, minimizing the impact of desiccation. This study contributes to understand the diversity of fungal communities in stone surfaces in subtropical settings and the dynamics of colonization on limestone.

Endolithic phototrophs in built and natural stone.

Lichens, algae and cyanobacteria have been detected growing endolithically in natural rock and in stone buildings in various countries of Australasia, Europe and Latin America. Previously these organisms had mainly been described in natural carbonaceous rocks in aquatic environments, with some reports in siliceous rocks, principally from extremophilic regions. Using various culture and microscopy methods, we have detected endoliths in siliceous stone, both natural and cut, in humid temperate and subtropical climates. Such endolithic growth leads to degradation of the stone structure, not only by mechanical means, but also by metabolites liberated by the cells. Using in vitro culture, transmission, optical and fluorescence microscopy, and confocal laser scanning microscopy, both coccoid and filamentous cyanobacteria and algae, including Cyanidiales, have been identified growing endolithically in the facades of historic buildings built from limestone, sandstone, granite, basalt and soapstone, as well as in some natural rocks. Numerically, the most abundant are small, single-celled, colonial cyanobacteria. These small phototrophs are difficult to detect by standard microscope techniques and some of these species have not been previously reported within stone.

Microbial biofilms on the sandstone monuments of the Angkor Wat Complex, Cambodia.

Discoloring biofilms from Cambodian temples Angkor Wat, Preah Khan, and the Bayon and West Prasat in Angkor Thom contained a microbial community dominated by coccoid cyanobacteria. Molecular analysis identified Chroococcidiopsis as major colonizer, but low similarity values (<95%) suggested a similar genus or species not present in the databases. In only two of the six sites sampled were filamentous cyanobacteria, Microcoleus, Leptolyngbya, and Scytonema, found; the first two detected by sequencing of 16S rRNA gene library clones from samples of a moist green biofilm on internal walls in Preah Khan, where Lyngbya (possibly synonymous with Microcoleus) was seen by direct microscopy as major colonizer. Scytonema was detected also by microscopy on an internal wall in the Bayon. This suggests that filamentous cyanobacteria are more prevalent in internal (high moisture) areas. Heterotrophic bacteria were found in all samples. DNA sequencing of bands from DGGE gels identified Proteobacteria (Stenotrophomonas maltophilia and Methylobacterium radiotolerans) and Firmicutes (Bacillus sp., Bacillus niacini, Bacillus sporothermodurans, Lysinibacillus fusiformis, Paenibacillus sp., Paenibacillus panacisoli, and Paenibacillus zanthoxyli). Some of these bacteria produce organic acids, potentially degrading stone. Actinobacteria, mainly streptomycetes, were present in most samples; algae and fungi were rare. A dark-pigmented filamentous fungus was detected in internal and external Preah Khan samples, while the alga Trentepohlia was found only in samples taken from external, pink-stained stone at Preah Khan. Results show that these microbial biofilms are mature communities whose major constituents are resistant to dehydration and high levels of irradiation and can be involved in deterioration of sandstone. Such analyses are important prerequisites to the application of control strategies.

Effect of culture medium on biocalcification by Pseudomonas Putida, Lysinibacillus Sphaericus and Bacillus Subtilis

The objective of this study is to investigate the efficiency of calcium carbonate bioprecipitation by Lysinibacillus sphaericus, Bacillus subtilis and Pseudomonas putida, obtained from the Coleção de Culturas do Instituto Nacional de Controle de Qualidade em Saúde (INCQS), as a first step in determining their potential to protect building materials against water uptake. Two culture media were studied: modified B4 containing calcium acetate and 295 with calcium chloride. Calcium consumption in the two media after incubation with and without the bacterial inoculum was determined by atomic absorption analysis. Modified B4 gave the best results and in this medium Pseudomonas putida INQCS 113 produced the highest calcium carbonate precipitation, followed by Lysinibacillus sphaericus INQCS 414; the lowest precipitation was produced by Bacillus subtilis INQCS 328. In this culture medium XRD analysis showed that Pseudomonas putida and Bacillus subtilis precipitated calcite and vaterite polymorphs while Lysinibacillus sphaericus produced only vaterite. The shape and size of the crystals were affected by culture medium, bacterial strain and culture conditions, static or shaken. In conclusion, of the three strains Pseudomonas putida INQCS 113 in modified B4 medium gave the best results precipitating 96 percent of the calcium, this strain thus has good potential for use on building materials.

Biocide-containing varnish for the protection of sandstone: comparison of formulations and laboratory test methods.

Two formulations of acrylic varnish, with and without either of two dry film biocides--one a mixture of isothiazolinones and benzimidazole derivatives, and the other a carbamate--were tested in vitro for their activity against mixtures of filamentous fungi and cyanobacteria found on sandstone buildings. Growth on filter-paper squares coated with the varnishes was assessed semi-quantitatively by naked eye, quantitatively by image analysis and chemically by measurement of ergosterol and chlorophyll a. The lower solvent content (higher resin) varnish was more inhibitory to cyanobacteria than the higher varnish content, whilst the opposite was true for the fungal inoculum. The carbamate biocide was effective against cyanobacteria, unlike the isothiazolinone mixture, but the latter produced more inhibition of fungal growth. The three assay methods produced generally similar results, although visual observation was obviously the most imprecise. There was an anomaly in the ergosterol measurements, which was considered to be caused by the varying ergosterol content and unequal inhibition of the three fungal genera used in the inoculum. Fusarium sp. was shown to contain higher levels of this membrane component than Cladosporium sp. and Penicillium sp. For this reason, the most appropriate method overall, giving reliable quantitative results, was deemed to be the image analysis.

Effect of culture medium on biocalcification by Pseudomonas Putida, Lysinibacillus Sphaericus and Bacillus Subtilis.

The objective of this study is to investigate the efficiency of calcium carbonate bioprecipitation by Lysinibacillus sphaericus, Bacillus subtilis and Pseudomonas putida, obtained from the Coleção de Culturas do Instituto Nacional de Controle de Qualidade em Saúde (INCQS), as a first step in determining their potential to protect building materials against water uptake. Two culture media were studied: modified B4 containing calcium acetate and 295 with calcium chloride. Calcium consumption in the two media after incubation with and without the bacterial inoculum was determined by atomic absorption analysis. Modified B4 gave the best results and in this medium Pseudomonas putida INQCS 113 produced the highest calcium carbonate precipitation, followed by Lysinibacillus sphaericus INQCS 414; the lowest precipitation was produced by Bacillus subtilis INQCS 328. In this culture medium XRD analysis showed that Pseudomonas putida and Bacillus subtilis precipitated calcite and vaterite polymorphs while Lysinibacillus sphaericus produced only vaterite. The shape and size of the crystals were affected by culture medium, bacterial strain and culture conditions, static or shaken. In conclusion, of the three strains Pseudomonas putida INQCS 113 in modified B4 medium gave the best results precipitating 96% of the calcium, this strain thus has good potential for use on building materials.

Biogenic black crusts on buildings in unpolluted environments.

Samples of peeling black crusts from modern and historic buildings in Campeche, Mexico, from a gravestone on the island of Dom Khon, Lao, and from the Anglican cathedral in Belize City were analyzed microbiologically, by scanning electron microscopy plus electron dispersive spectroscopy (EDS) and for pigment composition. In all cases, the surface was covered by a thick mat of cyanobacteria with dark brown sheaths. These were filamentous organisms of the genera Scytonema or Fischerella/Mastigocladus, except for one sample, where coccoid cyanobacteria of Subsection II were predominant. Fungi were not present at all sites and, where seen, were not the major biomass. High scytonemin:chlorophyll a ratios correlated with the dark pigmentation of the cyanobacterial cells and indicated the stressful conditions under which these organisms were living (high temperatures and ultraviolet levels, frequent desiccation). The absence, or low levels, of sulfur in the biofilms confirmed that there was little urban pollution at the sites and the EDS analysis showed that the black coloration was caused solely by cell pigmentation; no dark-colored elements were present at high concentrations. These results demonstrate that, unlike chemically formed thick black crusts found in polluted atmospheres, thin black crusts (which could be called patinas) in clean environments may be predominantly composed of filamentous cyanobacteria.

Cyanobacteria from Brazilian building walls are distant relatives of aquatic genera.

The 16S-rDNA from 22 cyanobacteria isolated from biofilms on walls of modern and historic buildings in Brazil was partially sequenced (approximately 350 bp) using specific primers. The cyanobacteria with the closest matching sequences were found using the BLAST tool. The sequences were combined with 52 other cyanobacterial sequences already deposited in public data banks and a dendrogram constructed, after deletion from each sequence of one of the variable 16S rDNA regions (VI). The newly sequenced organisms fitted well within their respective families, but their similarities to other members of the groups were generally low, less than 96%. Close matches were found only with one other terrestrial (hot dry desert) cyanobacterium, Microcoleus sociatus, and with Anabaena variabilis. Phylogenetic analysis suggested that the deletion of the hypervariable regions in the RNA structure is essential for meaningful evolutionary studies. The results support the standard phylogenetic tree based on morphology, but suggest that these terrestrial cyanobacteria are distant relatives of their equivalent aquatic genera and are, indeed, a distinct population.

Genes similar to naphthalene dioxygenase genes in trifluralin-degrading bacteria.

Trifluralin (alpha,alpha,alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) is a dinitroaniline compound which was first produced in the 1960s and has been used extensively as an agricultural herbicide. There are a few publications on the biodegradation of this xenobiotic compound, but to our knowledge nothing has been documented on the genetic aspects of its catabolism. In this article, we report the analysis of DNA isolated from bacteria previously shown to degrade trifluralin, using as probes the catabolic genes ndoB, todC, xyIX, catA and xyIE which encode the enzymes naphthalene 1,2-dioxygenase, toluene dioxygenase, toluate 1,2-dioxygenase, catechol 1,2-dioxygenase and catechol 2,3-dioxygenase respectively. Using PCR and hybridization analysis, the strong hybridization of the ndoB gene with DNA extracted from four trifluralin-degrading isolates was demonstrated, although none of them was able to degrade naphthalene, as indicated by the 'clear zone' test. The results indicated the presence in these bacteria of a dioxygenase gene, whose product could act on trifluralin as its principal substrate, or fortuitously, by cometabolism. This is the first publication on genes in trifluralin-degrading bacteria.

Algal and cyanobacterial biofilms on calcareous historic buildings.

Major microorganisms in biofilms on external surfaces of historic buildings are algae, cyanobacteria, bacteria, and fungi. Their growth causes discoloration and degradation. We compared the phototrophs on cement-based renderings and limestone substrates at 14 historic locations (47 sites sampled) in Europe and Latin America. Most biofilms contained both cyanobacteria and algae. Single-celled and colonial cyanobacteria frequently constituted the major phototroph biomass on limestone monuments (32 sites sampled). Greater numbers of phototrophs, and especially of algae and of filamentous morphotypes, were found on cement-based renderings (15 sites), probably owing to the porosity and small pore size of the latter substrates, allowing greater entry and retention of water. All phototrophic groups were more frequent on Latin American than on European buildings (20 and 27 sites, respectively), with cyanobacteria and filamentous phototrophs showing the greatest differences. The results confirm the influence of both climate and substrate on phototroph colonization of historic buildings.

Fungal colonization and succession on newly painted buildings and the effect of biocide.

This report describes the sequence of fungal colonization and the influence of biocide incorporation on paint films, determined using quantitative methods. Two buildings were painted with an acrylic paint, with and without an experimental biocide formulation containing a carbamate (carbendazin), N-octyl-2H-isothiazolin-3-one and N-(3,4-dichlorophenyl)N,N-dimethyl urea (total biocide concentration 0.25% w/w). One week after painting, the major groups of organisms detected were yeasts and Cladosporium. The yeast population fell to undetectable levels after the third week and this microbial group was not detected again until the 31st week, after which they increased to high levels on the 42nd week. Aureobasidium showed a pattern similar to the yeasts. The main fungal genera detected over the 42-week period were Alternaria, Curvularia, Epicoccum, Helminthosporium, Coelomycetes (mainly Pestalotia/Pestalotiopsis), Monascus, Nigrospora, Aureobasidium and Cladosporium. The latter was the main fungal genus detected at all times. The physiological factors controlling colonization are discussed. Cladosporium, Aureobasidium, Tripospermum and yeasts on the painted surfaces were all able to grow on mineral salts agar containing 10% sodium chloride. This is the first time that the genus Tripospermum has been reported on painted buildings. The fungal population on biocide-containing surfaces was significantly lower than on non-biocide-containing paint after 13 weeks and continued so to 42 weeks after painting, but there was no statistically significant difference in the level of fungal biodiversity.

Recent advances in the study of biocorrosion - an overview

Biocorrosion processes at metal surface are associated with microorganisms, or the products of their metabolic activities including enzymes, exopolymers, organic and inorganic acids, as well as volatile compounds such as ammonia or hydrogen sulfide. These can affect catholic and/or anodic reactions, thus altering electrochemistry at the biofilm/metal interface. Various mechanisms of biocorrosion, reflecting the variety of physiological activities carried out by different types of microorganisms, are identified and recent insights into these mechanisms reviewed. Many investigations have centered on the microbially-influenced corrosion of ferrous and copper alloys and particular microorganisms of interest have been the sulfate-reducing bacteria and metal (especially manganese)-depositing bacteria. The importance of microbial consortia and the role of extracellular polymeric substances in biocorrosion are emphasized. The contribution to the study of biocorrosion of modern analytical techniques, such as atomic force microscopy, Auger electron, X-ray photoelectron and Mössbauer spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy and microsensors, is discussed

Algae and cyanobacteria on painted surfaces in southerns Brazil

Algae and cyanobacteria disfigure the external surfaces of buildings and may cause their physico-chemical deterioration. Even though the climate in Brazil is humid, there is no published literature on this problem. The objective of this work was to identify the major photographs present on Brazilian constructions in residential, urban and rural sites. The algal and cyanobacterial types present on discolored surfaces of painted buildings in nine different municipalities in Brazil, all lying between latitudes 19§ South and 30§South, were examined. A total of 816 different organisms was detected in 58 sites. Approximately 63 (per cent) were single-celled or colonial organisms. The cyanobacterial genus, Synechocystis, was the most biodiverse and frequently comprised the major biomass. It was present in 63,4 (per cent) of sites. Second and third most frequently detected were Oscillatoria and the algal genus, Chorella, respectively. The latter organism showed the most widespread occurrence (72.4 per cent). Cyanobacteria were the most important colonizers, especially at urbans sites, where over 62 (per cent) of the organisms detected belonged to this class. Filamentous photographs were found in smaller numbers than non-filamentous at all locations.