Green, non-toxic and efficient adsorbent from hazardous ash waste for the recovery of valuable metals and heavy metal removal from waste streams.

As compared to alkali-activated geopolymers with phosphoric acid which may be used in high concentrations resulting in disposal concerns, acid-based geopolymers may have superior properties. A novel green method of converting waste ash to a geopolymer for use in adsorption applications such as water treatment is presented here. We use methanesulfonic acid, a green chemical with high acid strength and biodegradability to form geopolymers from coal and wood fly ashes.

Understanding the biological impact of organic pollutants absorbed by nanoplastics.

Many organisms are consuming food contaminated with micro- and nanoparticles of plastics, some of which absorb persistent organic pollutants (POPs) from the environment and acting as carrier vectors for increasing the bioavailability in living organisms. We recently reported that polymethylmethacrylate (PMMA) nanoparticles at low concentrations are not toxic to animal models tested. In this study, the toxicity of diphenylamine (DPA) incorporated PMMA nanoparticles are assessed using barnacle larvae as a model organism.

On the mechanism of marine fouling-prevention performance of oil-containing silicone elastomers.

For many decades, silicone elastomers with oil incorporated have served as fouling-release coating for marine applications. In a comprehensive study involving a series of laboratory-based marine fouling assays and extensive global field studies of up to 2-year duration, we compare polydimethylsiloxane (PDMS) coatings of the same composition loaded with oil via two different methods. One method used a traditional, one-pot pre-cure oil addition approach (o-PDMS) and another method used a newer post-cure infusion approach (i-PDMS).

Sewage sludge ash-based mortar as construction material: Mechanical studies, macrofouling, and marine toxicity.

Incinerated sewage sludge ash is tested here as a cement and aggregate substitute in mortar blocks. It can be used at various percentages to reduce the overall cost of production and promote ash recycling. The compressive strength of the cast blocks was tested at 28 days to determine the optimal combination of ball milled ash (replacing cement) and sewage sludge ash (replacing sand).

A comparative investigation of toxicity of three polymer nanoparticles on acorn barnacle (Amphibalanus amphitrite).

Pollution from plastic waste is increasingly prevalent in the environment and beginning to generate significant adverse impact on the health of living organisms. In this study, we investigate the toxicity of polymer nanoparticles exposed to Acorn Barnacle (Amphibalanus amphitrite) nauplii, as an animal model. Highly stable aqueous dispersion of luminescent nanoparticles from three common polymers: polymethylmethacrylate (PMMA), polystyrene (PS), and polyvinylchloride (PVC), were prepared via nanoprecipitation and fully characterised.

Ascidians collected during the 2013 Singapore Strait International Marine Biodiversity Workshop.

During the 2013 Singapore Strait International Marine Biodiversity Workshop, hundreds of ascidians were collected along with numerous other marine phyla. Collections were made intertidally as well as subtidally by snorkel, SCUBA, trawling and dredging. While many ascidian specimens remain unidentified, 14 aplousobranchs, nine phlebobranchs and 17 stolidobranchs have been identified; a surprising 50% of these comprise 20 new records for Singapore.

Incinerated Sewage Sludge Bottom Ash- Chemical processing, Leaching patterns and Toxicity testing.

Sewage sludge bottom ash, which is the major fraction obtained from the incineration of sewage sludge was treated with various organic and inorganic acids for heavy metal removal, along with a comparative phosphate treatment for heavy metal fixation. Malonic acid, an organic acid, was found to remove heavy metals better as compared to nitric acid, a strong inorganic acid. The acid treated samples were further examined for heavy metal leaching, followed by marine toxicity/abnormality testing of the leachates, where acid treated and phosphate treated ash leachate displayed higher (with malonic acid proving to be most toxic) and similar toxicity profiles as compared to raw ash leachate respectively.

Removal of larvae of two marine invasive bivalves, Mytilopsis sallei (Récluz, 1849) and Mytella strigata (Hanley, 1843), by water treatment processes.

The uptake and discharge of bivalve larvae through ballast water operations is a highly viable mechanism for transfer of shellfish. In this paper, we investigate the effects of common water treatment processes on the planktotrophic larvae of the two invasive species of shellfish, Mytilopsis sallei and Mytella strigata. The study found that common water treatment processes used in many ballast water treatment systems were effective for the removal of bivalve larvae, although later stages of larval forms required more effort to remove.

Evaluation of sewage sludge incineration ash as a potential land reclamation material.

This study evaluated the potential of utilising sewage sludge incineration ash as a land reclamation material. Toxicity assessment of the leachate of the ash was carried out for both terrestrial and marine organisms. Both the fruit fly Drosophila melanogaster and barnacle Amphibalanus amphitrite showed that both bottom and fly ash leached at liquid-to-solid (L/S) ratio 5 did not substantially affect viabilities.

Effect of Variations in Micropatterns and Surface Modulus on Marine Fouling of Engineering Polymers.

We report on the marine fouling and fouling release effects caused by variations of surface mechanical properties and microtopography of engineering polymers. Polymeric materials were covered with hierarchical micromolded topographical patterns inspired by the shell of the marine decapod crab Myomenippe hardwickii. These micropatterned surfaces were deployed in field static immersion tests.

Comparison of laboratory and field testing performance evaluations of siloxane-polyurethane fouling-release marine coatings.

A series of eight novel siloxane-polyurethane fouling-release (FR) coatings were assessed for their FR performance in both the laboratory and in the field. Laboratory analysis included adhesion assessments of bacteria, microalgae, macroalgal spores, adult barnacles and pseudobarnacles using high-throughput screening techniques, while field evaluations were conducted in accordance with standardized testing methods at three different ocean testing sites over the course of six-months exposure. The data collected were subjected to statistical analysis in order to identify potential correlations.

Measuring protein isoelectric points by AFM-based force spectroscopy using trace amounts of sample.

Protein charge at various pH and isoelectric point (pI) values is important in understanding protein function. However, often only trace amounts of unknown proteins are available and pI measurements cannot be obtained using conventional methods. Here, we show a method based on the atomic force microscope (AFM) to determine pI using minute quantities of proteins.

Antibacterial, electrospun nanofibers of novel poly(sulfobetaine) and poly(sulfabetaine)s.

Polymers capable of forming hydration layers have gained increasing attention due to their ability to form environmentally friendly antifouling surfaces. Zwitterionic polymers are an important class of materials under this category. However, the effectiveness of many zwitterionic polymers for long-term applications is compromised because of their solubility in sea water, poor hydrolytic stability and deteriorating mechanical integrity upon wetting.

Antifouling coatings based on covalently cross-linked agarose film via thermal azide-alkyne cycloaddition.

Coatings based on thin films of agarose-poly(ethylene glycol) (Agr-PEG) cross-linked systems are developed as environmentally-friendly and fouling-resistant marine coatings. The Agr-PEG cross-linked systems were prepared via thermal azide-alkyne cycloaddition (AAC) using azido-functionalized Agr (AgrAz) and activated alkynyl-containing poly(2-propiolamidoethyl methacrylate-co-poly(ethylene glycol)methyl ether methacrylate) P(PEMA-co-PEGMEMA) random copolymers as the precursors. The Agr-PEG cross-linked systems were further deposited onto a SS surface, pre-functionalized with an alkynyl-containing biomimetic anchor, dopamine propiolamide, to form a thin film after thermal treatment.

Tea stains-inspired initiator primer for surface grafting of antifouling and antimicrobial polymer brush coatings.

Inspired by tea stains, plant polyphenolic tannic acid (TA) was beneficially employed as the primer anchor for functional polymer brushes. The brominated TA (TABr) initiator primer was synthesized by partial modification of TA with alkyl bromide functionalities. TABr with trihydroxyphenyl moieties can readily anchor on a wide range of substrates, including metal, metal oxide, polymer, glass, and silicon.

Imprinting of metal receptors into multilayer polyelectrolyte films: fabrication and applications in marine antifouling.

Polymeric films constructed using the layer-by-layer (LbL) fabrication process were employed as a platform for metal ion immobilization and applied as a marine antifouling coating. The novel Cu ion imprinting process described is based on the use of metal ion templates and LbL multilayer covalent cross-linking. Custom synthesized, peptide mimicking polycations composed of histidine grafted poly(allylamine) (PAH) to bind metal ions, and methyl ester containing polyanions for convenient cross-linking were used in the fabrication process.

Polyion multilayers with precise surface charge control for antifouling.

We report on a molecular fabrication approach to precisely control surface ζ potentials of polymeric thin layers constructed by electrostatic layer-by-layer (LbL) assembly methods. The protocol established allows us to achieve surface isoelectric points (IEP) in the pH range of 6-10. Poly(acrylic acid) (PAA, a weak polyanion) and poly(diallyldimethylammonium chloride) (PDADMAC, a strong polycation) were chosen to build up the bulk films.

Barnacle larvae exploring surfaces with variable hydrophilicity: influence of morphology and adhesion of "footprint" proteins by AFM.

Interaction forces of adhesive proteins employed by cyprid larvae of Amphibalanus amphitrite for temporary attachment during surface exploration in marine fouling were studied by AFM force spectroscopy using chemically modified, reactive colloidal probes. The proteins were covalently attached to the surfaces of the probes by incubation in the protein deposits (footprints) left behind at the surface by the cyprids. This covalent coupling enabled robust and reproducible probing of adhesion of the attachment proteins to model surfaces with variable hydrophilicity.

Sulfobetaine-based polymer brushes in marine environment: is there an effect of the polymerizable group on the antifouling performance?

Three different zwitterionic polymer brush coatings for marine biofouling control were prepared by surface-initiated atom transfer radical polymerization (ATRP) of sulfobetaine-based monomers including methacrylamide (SBMAm), vinylbenzene (SBVB) and vinylimidazolium (SBVI). None of these brush systems have been assessed regarding marine antifouling performance. Antifouling tests performed indicate that surfaces featuring these three brush systems substantially reduce the adhesion of the marine microalgae, Amphora coffeaeformis, and the settlement of cyprid larvae of the barnacle, Amphibalanus amphitrite, in a similar way, displaying comparable performance.

Photoinduced anchoring and micropatterning of macroinitiators on polyurethane surfaces for graft polymerization of antifouling brush coatings.

Poly[3-azido-2-(2-bromo-2-methylpropanoyloxy)propyl methacrylate] (PAzBrMA) was synthesized as the macroinitiator and anchor for a functional polymer brush coating on polyurethane (PU) films. Ring-opening reaction of the epoxide group of poly(glycidyl methacrylate) with sodium azide produced the hydroxyl and azide functional groups. The hydroxyl groups were substituted with 2-bromoisobutyryl bromide to introduce the alkyl halide initiator.

Effect of ultrasound on cyprid footprint and juvenile barnacle adhesion on a fouling release material.

In our earlier studies, we have demonstrated that low and high intensity ultrasound can prevent barnacle cyprid settlement. In this study, we found that ultrasound treatment reduced the adhesion of newly metamorphosed barnacles up to 2 days' old. This was observed in the reduction of adhesion strength of the newly settled barnacles from ultrasound treated cyprids on silicone substrate compared to the adhesion strength of barnacles metamorphosed from cyprids not exposed to ultrasound.

Multilayers of fluorinated amphiphilic polyions for marine fouling prevention.

Sequential layer-by-layer (LbL) deposition of polyelectrolytes followed by chemical cross-linking was investigated as a method to fabricate functional amphiphilic surfaces for marine biofouling prevention applications. A novel polyanion, grafted with amphiphilic perfluoroalkyl polyethylene glycol (fPEG) side chains, was synthesized and subsequently used to introduce amphiphilic character to the LbL film. The structure of the polyanion was confirmed by FTIR and NMR.

Cross-linked polyelectrolyte multilayers for marine antifouling applications.

A polyionic multilayer film was fabricated by layer-by-layer (LbL) sequential deposition followed by cross-linking under mild conditions on a substrate surface to inhibit marine fouling. A novel polyanion, featuring methyl ester groups for an easy cross-linking was used as a generic solution for stabilization of LbL films in a harsh environment. Covalent cross-linking was confirmed by FTIR and XPS spectroscopy.