Effect of long-term storage and harvest site on the fatty acid profiles, mineral and antioxidant properties of selected edible Scottish seaweeds.

The limited understanding of the effect of pre-and post-harvest techniques still hinders the full exploitation of seaweed. Here, the effect of harvest site, long term storage and species on the elemental composition, fatty acid profile, lipid content, and antioxidant properties were determined in eight intertidal seaweed species common to Scotland, harvested for potential food application and stored for up to 128 weeks. Result showed that the most significant variation was due to species, with no statistical link found for the combined interaction effect of both storage duration and harvest site in most cases, except for the antioxidant parameters and some selected elements, which was limited to some seaweed species. Overall, our result showed that the chemical profiles of the seaweed species studied were remarkably consistent and unaffected by long term storage. Thus, suggesting that seaweeds sampled from Scotland could be a valuable resource for the development of functional foods.

Circular economy based landfill leachate treatment with sulphur-doped microporous biochar.

There is now increasing interest in the creation of a more 'circular economy', with a particular aim to eliminate waste - by design, within which products are optimised to be reused, restored or returned. Here, a sulphur functionalised microporous biochar was synthesised from an abundant biomass waste material (cherry kernels), for the selective removal of Pb(II) from landfill leachate as a representative heavy metal. The production process utilises renewable waste material and removes toxic chemicals. Characterisation of the biochar showed that pyrolysis and functionalisation formed an adsorbent with a microporous structure and rich surface chemical functionality. The adsorption process was optimised using a 'response surface methodology - Box-Behnken Design'. Lead removal efficiency approached 99.9% under optimised experimental conditions, i.e., where the solution pH was 6.0, the biochar dose was 4.0 g/L and the contact time was 47 min. The adsorption process was best described using a Freundlich model. The maximum amount of Pb(II) adsorbed was 44.92 mg/g. The main adsorption mechanisms occurred through outer-sphere (electrostatic attraction) and inner-sphere complexation. Desorption studies showed that three successful regeneration cycles (with acidic deionised water) could be used post pyrolysis. The biochar removed 97% of Pb(II) from landfill leachate samples, as compared to 9.4%, and 7.6% for two commercial activated carbon adsorbents. These findings demonstrate the high selectivity of this biochar towards Pb(II) and its applicability even in the presence of high concentrations of many potentially interfering inorganic and organic ions and compounds.

A review of the potential utilisation of plastic waste as adsorbent for removal of hazardous priority contaminants from aqueous environments.

There is growing global awareness of the presence and negative impacts of waste plastic in the marine environment. Risks to wildlife include ingestion and entanglement for macro-plastic (larger than 5 mm in length), alongside food chain transfer for micro-plastics (less than 5 mm in length). Plastics in the marine environment have also been shown to adsorb and accumulate contaminants from seawater, e.g., heavy metals and hydrophobic organic compounds. This means that plastics can additionally act as vectors for transport of contaminants, permitting ecotoxicological risks to be spatially extended. However, the ability of waste plastic to adsorb pollutants also offers potential opportunity, if they can be used for the decontamination of wastewater. Here, we provide an overview of marine plastic types and distribution, and then systematically assess their potential to be repurposed as novel adsorbents. Data published in recent years are interrogated to gain an overview of the interaction mechanisms between marine plastics and both organic and inorganic contaminants. In addition, factors that may be exploited to enhance their performance in removal of contaminants are also reviewed and prioritised, e.g., surface modification and activation. This paper highlights the novel potential of repurposing plastic waste for wastewater treatment applications and seeks to identify key knowledge gaps and future research priorities for scientists and engineers.

Source apportionment and risk assessment of emerging contaminants: an approach of pharmaco-signature in water systems.

This paper presents a methodology based on multivariate data analysis for characterizing potential source contributions of emerging contaminants (ECs) detected in 26 river water samples across multi-scape regions during dry and wet seasons. Based on this methodology, we unveil an approach toward potential source contributions of ECs, a concept we refer to as the "Pharmaco-signature." Exploratory analysis of data points has been carried out by unsupervised pattern recognition (hierarchical cluster analysis, HCA) and receptor model (principal component analysis-multiple linear regression, PCA-MLR) in an attempt to demonstrate significant source contributions of ECs in different land-use zone. Robust cluster solutions grouped the database according to different EC profiles. PCA-MLR identified that 58.9% of the mean summed ECs were contributed by domestic impact, 9.7% by antibiotics application, and 31.4% by drug abuse. Diclofenac, ibuprofen, codeine, ampicillin, tetracycline, and erythromycin-H2O have significant pollution risk quotients (RQ>1), indicating potentially high risk to aquatic organisms in Taiwan.

Introduction of human pharmaceuticals from wastewater treatment plants into the aquatic environment: a rural perspective.

Incomplete removal of pharmaceuticals during wastewater treatment can result in their discharge into the aquatic environment. The discharge of pharmaceuticals in wastewater treatment plant (WWTP) effluents into rivers, lakes and the oceans has led to detectable concentrations of pharmaceuticals in the aquatic environment in many countries. However, to date studies of WWTP discharges into the aquatic environment have largely been confined to areas of relatively high population density, industrial activity or systems impacted on by such areas. In this work, two sites in the far north of Scotland were used to assess whether, and which, pharmaceuticals were being introduced into natural waters in a rural environment with low population density. Samples from two WWTPs (with differing modes of operation), and one receiving water, the River Thurso, were analysed for the presence of 12 pharmaceuticals (diclofenac, clofibric acid, erythromycin, ibuprofen, mefenamic acid, paracetamol, propranolol, sulfamethoxazole, tamoxifen, trimethoprim and dextropropoxyphene). Ten of the 12 pharmaceuticals investigated were detected in at least one of the 40 WWTP effluent samples. Maximum concentrations ranged from 7 ng L(-1) (sulfamethoxazole) to 22.8 µg L(-1) (paracetamol) with diclofenac and mefenamic acid being present in all of samples analysed at concentrations between 24.2 and 927 ng L(-1) and 11.5 and 22.8 µg L(-1), respectively. Additionally, the presence of four pharmaceuticals at ng L(-1) levels in the River Thurso, into which one of the WWTPs discharges, shows that such discharges result in measurable levels of pharmaceuticals in the environment. This provides direct evidence that, even in rural areas with low population densities, effluents from WWTPs can produce quantifiable levels of human pharmaceutical in the natural aquatic environment. These observations indicate that human pharmaceuticals may be considered as contaminants, with potential to influence water quality, management and conservation not only in urban and industrial regions but also those more rural in nature.

Metabolite profile shifts in the heathland lichen Cladonia portentosa in response to N deposition reveal novel biomarkers.

The heathland lichen Cladonia portentosa was collected from sites in mainland Britain differing either in rates of wet N deposition or in annual mean N concentration in rainfall based on a modelled data set. Methanolic extracts of thalli were analyzed by liquid chromatography time-of-flight mass spectrometry to yield metabolic profiles. Differences between sites in metabolite concentration were quantified using multivariate statistical tools and used to identify potential biomarker molecules. The abundances of three structurally related betaine lipids showed an increase with increasing modelled N deposition to a threshold of 22.3 kg ha(-1) year(-1) after which they remained constant. In contrast, the abundance of a phosphatidylcholine (PC) lipid showed concomitant decrease. Correlations of the identified biomarkers with N deposition and precipitation were stronger than those with N concentrations. The results presented in this study clearly show that N enrichment associated with tissue P limitation changes lipid composition, leading to shifts from PCs to betaine lipids, and that these lipids identified have the potential to be used as biomarkers for nitrogen enrichment.

Quantification of human pharmaceuticals in water samples by high performance liquid chromatography-tandem mass spectrometry.

An improved analytical method for determination of human pharmaceuticals in natural and wastewaters with ng L(-1) sensitivity is presented. The method is applicable to pharmaceuticals from a wide range of therapeutic classes including antibiotics, analgesics, anti-inflammatories and anti-cancer compounds. Pharmaceuticals were extracted from waters using solid-phase extraction, and after concentration, analysed by high performance liquid chromatography with tandem mass spectrometric detection (HPLC-MS/MS). Identification of each compound was secured using retention time and by the selected reaction monitoring of two transitions, one of which was additionally used for quantification. Limits of detection ranged from 0.03 to 0.96 ng L(-1) and were up to two orders of magnitude lower than those of previously published methods. The method was validated using spiked samples prepared from tap, river and sea water as well as wastewater effluents, collected from the North of Scotland. Analysis of wastewater effluents revealed the presence of mefenamic acid, ibuprofen, erythromycin, diclofenac and trimethoprim. None of the selected pharmaceuticals were detected in river, tap or sea water samples.

The development of a marine natural product-based antifouling paint.

Problems with tin and copper antifouling compounds have highlighted the need to develop new environmentally friendly antifouling coatings. Bacteria isolated from living surfaces in the marine environment are a promising source of natural antifouling compounds. Four isolates were used to produce extracts that were formulated into ten water-based paints. All but one of the paints showed activity against a test panel of fouling bacteria. Five of the paints were further tested for their ability to inhibit the settlement of barnacle larvae, Balanus amphitrite, and algal spores of Ulva lactuca, and for their ability to inhibit the growth of U. lactuca. Two paints caused a significant decrease in the number of settled barnacles. One paint containing extract of Pseudomonas sp. strain NUDMB50-11, showed excellent activity in all assays. The antifouling chemicals responsible for the activity of the extract were isolated, using bioassay guided fractionation, and their chemical structures determined.

Biofilm-specific cross-species induction of antimicrobial compounds in bacilli.

An air-membrane surface (AMS) bioreactor was designed to allow bacteria to grow attached to a surface as a biofilm in contact with air. When Bacillus licheniformis strain EI-34-6, isolated from the surface of a marine alga, was grown in this reactor, cells produced antimicrobial compounds which they did not produce when they were grown in shake flask cultures. An unidentified red pigment was also produced by surface-grown cells but not by planktonically grown cells. Glycerol and ferric iron were important for the production of antimicrobial compounds and the red pigment. Release of these secondary metabolites was not due to the onset of sporulation. Cell-free spent medium recovered from beneath the reactor membrane could induce production of antimicrobial compounds and red pigment in shake flask cultures. Neither glycerol nor ferric iron was required for production of these inducer compounds. Spent medium from beneath the membrane of an AMS bioreactor culture of Bacillus subtilis strain DSM10(T) and Bacillus pumilus strain EI-25-8 could also induce production of antimicrobial compounds and a red pigment in B. licheniformis isolate EI-34-6 grown in shake flask cultures; however, the corresponding spent medium from shake flask cultures of DSM10(T) and EI-25-8 could not. These results suggest that there is a biofilm-specific cross-species signaling system which can induce planktonically grown cells to behave as if they were in a biofilm by regulating the expression of pigments and antimicrobial compounds.

Biodegradation of crude oil across a wide range of salinities by an extremely halotolerant bacterial consortium MPD-M, immobilized onto polypropylene fibers.

The bacterial consortium MPD-M, isolated from sediment associated with Colombian mangrove roots, was effective in the treatment of hydrocarbons in water with salinities varying from 0 to 180 g L(-1). Where the salinity of the culture medium surpassed 20 g L(-1), its effectiveness increased when the cells were immobilized on polypropylene fibers. Over the range of salinity evaluated, the immobilized cells significantly enhanced the biodegradation rate of crude oil compared with free-living cells, especially with increasing salinity in the culture medium. Contrary to that observed in free cell systems, the bacterial consortium MPD-M was highly stable in immobilized systems and it was not greatly affected by increments in salinity. Biodegradation was evident even at the highest salinity evaluated (180 g L(-1)), where biodegradation was between 4 and 7 times higher with immobilized cells compared to free cells. The biodegradation of pristane (PR) and phytane (PH) and of the aromatic fraction was also increased using cells immobilized on polypropylene fibers.

JM47, a cyclic tetrapeptide HC-toxin analogue from a marine Fusarium species.

The known metabolite, enniatin B, and a cyclic tetrapeptide, JM47, which is a new natural product, were extracted from brown rice cultures of a marine fungus, identified as a Fusarium species, isolated from the marine alga Codium fragile. NMR studies, including 15N HMQC and 15N HMBC, established the structure of JM47 as cyclo(Ala-Ala-Aoh-Pro), where Aoh is the amino acid, (2S,9S)-2-amino-8-oxo-9-hydroxydecanoic acid. The absolute stereochemistry of the Aoh side chain carbinol centre was determined using Mosher ester methodology. Analysis of NOESY data assisted by molecular modelling revealed an alternating L-, D-, L-, D-configuration for the tetrapeptide core. The absolute stereochemistry of the core was determined by acidic hydrolysis and chiral TLC analysis of the proline residue. JM47 belongs to the HC-toxin family of cyclic tetrapeptides which possess a 2-amino-8-oxo-9,10-epoxydecanoic acid residue in place of the Aoh unit. This is the first report of an analogue of HC-toxin from a marine Fusarium species.

Surface attachment induced production of antimicrobial compounds by marine epiphytic bacteria using modified roller bottle cultivation.

A modified roller bottle culture method elicited the production of antimicrobial compounds from 2 epibiotic marine bacterial strains, EI-34-6 and II-111-5, isolated from the surface of the marine alga Palmaria palmata. These isolates, tentatively identified as Bacillus species, were grown as a biofilm on the surface of nutrient glycerol ferric agar (NGFA) and marine Columbia glycerol agar (MCGA) on the inside of a rolling bottle. The biofilm was shown to be stable, and the cells were difficult to remove from the agar surface. The culture supernatant exhibited a different antibiotic spectrum when the strains were grown using the agar roller bottle method compared with shake flask cultures or nonagar roller bottle cultures. These results suggest that biofilm formation is an important factor in the production of antimicrobial compounds by these 2 strains, and roller bottle cultivation also allowed production of these compounds to be increased. The methodology used here has the potential to allow increased production of useful secondary metabolites such as antibiotics from marine epibiotic bacteria.