Graphene oxide-based degradation of metaldehyde : effective oxidation through a modified Fenton's Process

A modified graphene oxide-based Fenton’s reaction has been investigated for the degradation of a challenging emerging contaminant which is not effectively removed in conventional water treatment. Metaldehyde, used as the challenge molecule in this study, is a common molluscicide that (like many highly soluble contaminants) has frequently breached European regulatory limits in surface waters. The new method involves graphene with higher hydrophilic characteristics (single-layer graphene oxide, SLGO) as a system that participates in a redox reaction with hydrogen peroxide and which can potentially stabilize the radical dotOH generated, which subsequently breaks down organic contaminants. The modified Fenton’s reaction has shown to be effective in degrading metaldehyde in natural waters (>92% removal), even at high contaminant concentrations (50 mg metaldehyde/L) and in the presence of high background organic matter and dissolved salts. The reaction is relatively pH insensitive. SLGO maintained its catalytic performance over 3 treatment cycles when immobilized. Its performance gradually decreased over time, reaching around 50% of starting performance on the 10th treatment cycle. X-ray photoelectron spectroscopy (XPS) analysis of modifications caused in SLGO by the oxidizing treatment indicated that the oxidation of Csingle bondC sp2 to carbonyl groups may be the cause of the decrease in performance. The proposed modified Fenton’s process has the potential to substitute traditional Fenton’s treatment although regeneration of the nanocarbon is required for its prolonged use

A simple method for the production of large volume 3D macroporous hydrogels for advanced biotechnological, medical and environmental applications

The development of bulk, three-dimensional (3D), macroporous polymers with high permeability, large surface area and large volume is highly desirable for a range of applications in the biomedical, biotechnological and environmental areas. The experimental techniques currently used are limited to the production of small size and volume cryogel material. In this work we propose a novel, versatile, simple and reproducible method for the synthesis of large volume porous polymer hydrogels by cryogelation. By controlling the freezing process of the reagent/polymer solution, large-scale 3D macroporous gels with wide interconnected pores (up to 200??m in diameter) and large accessible surface area have been synthesized. For the first time, macroporous gels (of up to 400?ml bulk volume) with controlled porous structure were manufactured, with potential for scale up to much larger gel dimensions. This method can be used for production of novel 3D multi-component macroporous composite materials with a uniform distribution of embedded particles. The proposed method provides better control of freezing conditions and thus overcomes existing drawbacks limiting production of large gel-based devices and matrices. The proposed method could serve as a new design concept for functional 3D macroporous gels and composites preparation for biomedical, biotechnological and environmental applications

The evolution of embryonic creek systems in a recently inundated large open coast managed realignment site

Managed realignment (MR) schemes are being implemented to compensate for the degradation of coastal habitats. However, evidence suggests that MR sites have lower biodiversity than anticipated, which has been linked to poor drainage. Despite creek networks playing an important role in enhancing site drainage in natural intertidal environments, there remains a shortage of data on the formation and evolution of creeks within MR sites. This study evaluates creek development at the Medmerry Managed Realignment Site, UK. Creek development is investigated using differential global positioning system(dGPS) data, supported by sedimentological analyses and a high-resolution digital surface model (DSM) derived from images taken using a small unmanned aerial vehicle. Measurements indicated that creeks will develop relatively quickly, but are influenced by differences in the sub-surface sedimentological conditions. A suitable level of agreement was found between the DSM and dGPS measurements, demonstrating the appropriateness of this method to study creek development within intertidal environments at a higher resolution than traditional surveying techniques. These results are used to propose the collapseof sub-surface piping as the primary creek formation mechanism. Findings are discussed in terms of increasing the success of MR schemes and enhancing site design to maximise the ecosystem services provided

Electrokinetic generation of iron-rich barriers in soils:realising the potential for nuclear site management and decommissioning

Following earlier field-scale pilot work on nuclear site materials in the late 2000s, there has recently been renewed research and industry interest in the application of electrokinetic technologies for nuclear site management and remediation in the UK. One relatively novel application of electrokinetics is the use of sacrificial steel electrodes (coupled with an in situ generated pH-Eh gradient in the treated material) to precipitate sub-surface iron-rich barriers for groundwater and/or leachate containment, which could be used to grout or contain contaminated fluids in the sub-surface on working nuclear sites or sites undergoing decommissioning. Here, we report previously unpublished data from two work programmes exploring the higher Technology Readiness Level (TRL) application of this electrokinetic iron-barrier approach to materials typical of those found in the subsurface of the Sellafield nuclear licensed site, UK. The first programme, funded by the UK National Nuclear Laboratory (NNL), assessed the electrokinetic generation of iron-rich barriers at metre + scale in simulated Sellafield materials, while the second programme, funded under the current UK TRANSCEND consortium project, examined electrokinetic iron-barrier formation at smaller (&lt;1 m) scale, but in real site materials. Both programmes indicate that iron-rich barriers can be conveniently and electrokinetically grown in different geometries over reasonable timescales (months) in realistic site subsurface materials (sands), in electrolytes similar to natural waters found in the environment. Voltage requirements are low (&lt;1 V cm−1) with energy and consumables costs of no more than single-digit or tens of US dollars at the metre-plus scale. Further work is needed however to assess the longevity of the iron precipitates forming the subsurface barrier, and to explore barrier generation at the geometries and scales required for (site specific) field application.</p

Sediment structure and physicochemical changes following tidal inundation at a large open coast managed realignment site

Managed realignment (MR) schemes are being implemented to compensate for the loss of intertidal saltmarsh habitats by breaching flood defences and inundating the formerly defended coastal hinterland. However, studies have shown that MR sites have lower biodiversity than anticipated, which has been linked with anoxia and poor drainage resulting from compaction and the collapse of sediment pore space caused by the site's former terrestrial land use. Despite this proposed link between biodiversity and soil structure, the evolution of the sediment sub-surface following site inundation has rarely been examined, particularly over the early stages of the terrestrial to marine or estuarine transition. This paper presents a novel combination of broad- and intensive-scale analysis of the sub-surface evolution of the Medmerry Managed Realignment Site (West Sussex, UK) in the three years following site inundation. Repeated broad-scale sediment physiochemical datasets are analysed to assess the early changes in the sediment subsurface and the preservation of the former terrestrial surface, comparing four locations of different former land uses. Additionally, for two of these locations, high-intensity 3D-computed X-ray microtomography and Itrax micro-X-ray fluorescence spectrometry analyses are presented. Results provide new data on differences in sediment properties and structure related to the former land use, indicating that increased agricultural activity leads to increased compaction and reduced porosity. The presence of anoxic conditions, indicative of poor hydrological connectivity between the terrestrial and post-inundation intertidal sediment facies, was only detected at one site. This site has experienced the highest rate of accretion over the terrestrial surface (ca. 7 cm over 36 months), suggesting that poor drainage is caused by the interaction (or lack of) between sediment facies rather than the former land use. This has significant implications for the design of future MR sites in terms of preparing sites, their anticipated evolution, and the delivery of ecosystem services

A cryogel-based bioreactor for water treatment applications

The aim of this study was to develop and test a non-diffusion limited, high cell density bioreactor for biodegradation of various phenol derivatives. The bioreactor was obtained using a straightforward one-step preparation method using cryostructuration and direct cross-linking of bacteria into a 3D structured (sponge-like) macroporous cryogel composite material consisting of 11.6% (by mass) cells and 1.2–1.7% polymer, with approximately 87% water (in the material pores). The macroporous cryogel composite material, composed of live bacteria, has pore sizes in the range of 20–150 μm (confirmed by SEM and Laser Scanning Confocal Microscopy). The enzymatic activity of bacteria within the cryogel structure and the effect of freezing on the viability of the cross-linked cells was estimated by MTT assay. Cryogels based on Pseudomonas mendocina, Rhodococcus koreensis and Acinetobacter radioresistens were exploited for the effective bioremediation of phenol and m-cresol, and to a lesser extent 2-chlorophenol and 4-chlorophenol, utilising these phenolic contaminants in water as their only source of carbon. For evaluation of treatment scalability the bioreactors were prepared in plastic “Kaldnes” carriers to improve their mechanical properties and allow application in batch or fluidised bed water treatment modes.</p

Identification of tidal trapping of microplastics in a temperate salt marsh system using sea surface microlayer sampling

Microplastics are contaminants of increasing global environmental concern. Estuaries are a major transport pathway for land-derived plastics to the open ocean but are relatively understudied compared to coastal and open marine environments. The role of the “estuarine filter”, by which the supply of sediments and contaminants to the sea is moderated by processes including vegetative trapping and particle flocculation, remains poorly defined for microplastics land to sea transfer. Here, we focus on the sea surface microlayer (SML) as a vector for microplastics, and use SML sampling to assess microplastic trapping in a temperate marsh system in Southampton Water, UK. The SML is known to concentrate microplastics relative to the underlying water and is the first part of rising tidal waters to traverse intertidal and upper tidal surfaces. Sampling a salt marsh creek at high temporal resolution allowed assessment of microplastics in-wash and outflow from the salt marsh, and its relationship with tidal state and bulk suspended sediment concentrations (SSC), over spring and neap tides. A statistically significant decrease in microplastics abundance from the flood tide to the ebb tide was found, and a weak positive relationship with SSC observed

Validation of a method to quantify microfibres present in aquatic surface microlayers

Many of the methods for microplastics quantification in the environment are criticised creating problems with data validity. Quantification of microplastics in the surface microlayer of aquatic environments using glass plate dipping holds promise as a simple field method, but its efficiency has yet to be validated. We tested a standard glass plate dipping method to assess recovery of four common polymer microfibres and two common natural fibres, under three different salinities (freshwater, brackish water, saltwater). Overall recovery rates were low (26.8 ± 1.54%) but higher recoveries were observed under saltwater treatments (36.5 ± 3.01%) than brackish water (24.5 ± 1.92%) or freshwater (19.3 ± 1.92%). The fibre types showed different recovery rates, with acrylic yielding significantly higher recovery rates (37.0 ± 2.71%) than other fibres across treatments. No clear relationship between the density of the fibres and the recovery efficiency was seen. We suggest that, where this method is used for monitoring microplastics, the results will typically underestimate the total amount present, but that recovery is sufficiently consistent to allow comparison of differences between sampling locations. When comparing data across river-estuarine or similar transects salinity should be monitored to account for salinity-induced differences in sampling recovery

Trends in the recovery of phosphorus in bioavailable forms from wastewater

Addressing food security issues arising from phosphorus (P) scarcity is described as one of the greatest global challenges of the 21st Century. Dependence on inorganic phosphate fertilisers derived from limited geological sources of P creates an urgent need to recover P from wastes and treated waters, in safe forms that are also effective agriculturally – the established process of P removal by chemical precipitation using Fe or Al salts, is effective for P removal but leads to residues with limited bioavailability and contamination concerns. One of the greatest opportunities for P recovery is at wastewater treatment plants (WWTPs) where the crystallisation of struvite and Ca-P from enhanced biological P removal (EBPR) sludge is well developed and already shown to be economically and operationally feasible in some WWTPs. However, recovery through this approach can be limited to &lt;25% efficiency unless chemical extraction is applied. Thermochemical treatment of sludge ash produces detoxified residues that are currently utilised by the fertiliser industry; wet chemical extraction can be economically feasible in recovering P and other by-products. The bioavailability of recovered P depends on soil pH as well as the P-rich material in question. Struvite is a superior recovered P product in terms of plant availability, while use of Ca-P and thermochemically treated sewage sludge ash is limited to acidic soils. These technologies, in addition to others less developed, will be commercially pushed forward by revised fertiliser legislation and foreseeable legislative limits for WWTPs to achieve discharges of &lt;1 mg P/L

Assessing the role of the "estuarine filter" for emerging contaminants : pharmaceuticals, perfluoroalkyl compounds and plasticisers in sediment cores from two contrasting systems in the southern U.K.

The environmental occurrence, fate and ecotoxicity of emerging contaminants (ECs) has been the subject of increasing research, policy and public concern over the past two decades. While a wide range of publications have examined the environmental persistence and sediment/soil interactions of ECs following their discharge into aquatic environments, the extent to which ECs are sequestered in estuarine sediments, and the impact of this on their environmental persistence and supply to the ocean, in comparison remains unclear. This Article examines the environmental concentrations of seven, relatively water-soluble and environmentally mobile, ECs (including pharmaceuticals, perfluoroalkyl compounds, and plasticisers) in dated intertidal saltmarsh cores from two contrasting estuarine sites in the southern U.K. (one heavily urbanised/industrial, the other non-urbanised). Mean sediment EC concentrations are similar in both estuarine systems (in the range 0.1 (acetaminophen) to 17 (4-hydroxyacetophenone) ng/g dry weight). Despite their variable reported Log Kow values (from ca. 0.5 to > 7), the ECs are all apparently mobile in the marsh systems studied, and where subsurface concentration maxima are present these most likely relate to local flushing or diffusive processes and cannot be clearly linked to likely input trends or changes in sediment geochemistry (including sedimentary organic carbon content). The “estuarine filter” here, at least with respect to intertidal saltmarsh sediments, shows reduced potential to sequester the seven ECs examined and mediate their supply to coastal and shelf environments