Biodegradation of chitosan and its effect on metal bioavailability.

The microbial breakdown of chitosan, a fishery waste-based material, and its derivative cross-linked chitosans, in both non-contaminated and contaminated conditions was investigated in a laboratory incubation study. Biodegradation of chitosan and cross-linked chitosans was affected by the presence of heavy metals. Zn was more pronounced in inhibiting microbial activity than Cu and Pb. It was estimated that a longer period is required to complete the breakdown of the cross-linked chitosans (up to approximately 100 years) than unmodified chitosan (up to approximately 10 years). The influence of biodegradation on the bioavailable fraction of heavy metals was studied concurrently with the biodegradation trial. It was found that the binding behaviour of chitosan for heavy metals was not affected by the biodegradation process.

Treatment of heavy metals by iron oxide coated and natural gravel media in Sustainable urban Drainage Systems.

Sustainable urban Drainage Systems (SuDS) filter drains are simple, low-cost systems utilized as a first defence to treat road runoff by employing biogeochemical processes to reduce pollutants. However, the mechanisms involved in pollution attenuation are poorly understood. This work aims to develop a better understanding of these mechanisms to facilitate improved SuDS design. Since heavy metals are a large fraction of pollution in road runoff, this study aimed to enhance heavy metal removal of filter drain gravel with an iron oxide mineral amendment to increase surface area for heavy metal scavenging. Experiments showed that amendment-coated and uncoated (control) gravel removed similar quantities of heavy metals. Moreover, when normalized to surface area, iron oxide coated gravels (IOCGs) showed poorer metal removal capacities than uncoated gravel. Inspection of the uncoated microgabbro gravel indicated that clay particulates on the surface (a natural product of weathering of this material) augmented heavy metal removal, generating metal sequestration capacities that were competitive compared with IOCGs. Furthermore, when the weathered surface was scrubbed and removed, metal removal capacities were reduced by 20%. When compared with other lithologies, adsorption of heavy metals by microgabbro was 10-70% higher, indicating that both the lithology of the gravel, and the presence of a weathered surface, considerably influence its ability to immobilize heavy metals. These results contradict previous assumptions which suggest that gravel lithology is not a significant factor in SuDS design. Based upon these results, weathered microgabbro is suggested to be an ideal lithology for use in SuDS.

Metal accumulation in Lolium perenne and Brassica napus as affected by application of chitosans.

The effects of chitosan, a fishery waste-based material, and its derivative glutaraldehyde cross-linked chitosan (chitosan-GLA) on metal uptake by Lolium perenne (perennial ryegrass) and Brassica napus (rapeseed) were studied in a greenhouse pot experiment. Metal uptake by perennial ryegrass was highly dependent on the rate of addition of the chitosans. Low application rate (1% w/w) enhanced metal uptake, whereas 10% (w/w) addition decreased metal uptake. It was estimated that chitosan 1% (w/w) treatment could assist perennial ryegrass to remove approximately 3.2 kg Zn/ha and 0.29 kg Pb/ha. For rapeseed, metal uptake was decreased at all rates of application of chitosans. The ammonium acetate extractable metals in soil decreased following application of chitosans and plant growth.

Carbonised red mud--a new water treatment product made from a waste material.

Proposals to use red mud, the waste produced by the extraction of alumina from bauxite ore in the Bayer process, as a material for treatment of heavy metal-contaminated water are limited by its inherent alkalinity and variability. Attempts to lower its pH have been largely unreliable. However, an alternative strategy is carbonisation of red mud by catalytic hydrocarbon cracking, which results in a magnetic material of greater surface area. The efficacy of this material has been compared with that of the untreated parent red mud and acidified red mud for the sorption of CrO(4)(2-), Cu(2+) and Pb(2+). Carbonised red mud does not remove CrO(4)(2-) from solution, but shows enhancement of Cu(2+) and Pb(2+) removal. There is an approximate ten-fold increase in removal of Cu(2+) and Pb(2+) by carbonised red mud compared with acidified red mud.

Spatial and temporal variations in Pb concentrations and isotopic composition in road dust, farmland soil and vegetation in proximity to roads since cessation of use of leaded petrol in the UK.

Results are presented for a study of spatial distributions and temporal trends in concentrations of lead (Pb) from different sources in soil and vegetation of an arable farm in central Scotland in the decade since the use of leaded petrol was terminated. Isotopic analyses revealed that in all of the samples analysed, the Pb conformed to a binary mixture of petrol Pb and Pb from industrial or indigenous geological sources and that locally enhanced levels of petrol Pb were restricted to within 10 m of a motorway and 3 m of a minor road. Overall, the dominant source of Pb was historical emissions from nearby industrial areas. There was no discernible change in concentration or isotopic composition of Pb in surface soil or vegetation over the decade since the ban on the sale of leaded petrol. There was an order of magnitude decrease in Pb concentrations in road dust over the study period, but petrol Pb persisted at up to 43% of the total Pb concentration in 2010. Similar concentrations and spatial distributions of petrol Pb and non petrol Pb in vegetation in both 2001 and 2010, with enhanced concentrations near roads, suggested that redistribution of previously deposited material has operated continuously over that period, maintaining a transfer pathway of Pb into the biosphere. The results for vegetation and soil transects near minor roads provided evidence of a non petrol Pb source associated with roads/traffic, but surface soil samples from the vicinity of a motorway failed to show evidence of such a source.

Binding of heavy metal contaminants onto chitosans--an evaluation for remediation of metal contaminated soil and water.

The binding efficiency of chitosan samples for Ag(+), Cd(2+), Cu(2+), Pb(2+) and Zn(2+) has been evaluated in order to consider their application to remediate metal contaminated soil and water. The sorption behaviour of metal ions was assessed using a batch technique at different contact time and initial metal concentration with different background electrolytes. The kinetics followed a pseudo-second-order model, while the equilibrium data correlated well with the Freundlich and Langmuir isotherm models. For example, the maximum sorption capacity (Q) for chitosan was estimated as 1.93 mmol/g for Ag(+), 1.61 mmol/g for Cu(2+), 0.94 mmol/g for Zn(2+), 0.72 mmol/g for Cd(2+) and 0.64 mmol/g for Pb(2+). Covalent interaction between metal ions and functional groups (amino and hydroxyl) of the chitosans was the main binding mechanism. Ion exchange is not an important process. Chitosan and cross-linked chitosans were able to bind metal ions in the presence of K(+), Cl(-) and NO(3)(-). The nature of Cl(-) and NO(3)(-) ions did not affect Zn(2+) binding by the chitosans. Even at 11x dilution, the chitosans were able to retain metal ions on their surfaces.

Analytical and sampling constraints in ²¹°Pb dating.

²¹°Pb dating provides a valuable, widely used means of establishing recent chronologies for sediments and other accumulating natural deposits. The Constant Rate of Supply (CRS) model is the most versatile and widely used method for establishing ²¹°Pb chronologies but, when using this model, care must be taken to account for limitations imposed by sampling and analytical factors. In particular, incompatibility of finite values for empirical data, which are constrained by detection limit and core length, with terms in the age calculation, which represent integrations to infinity, can generate erroneously old ages for deeper sections of cores. The bias in calculated ages increases with poorer limit of detection and the magnitude of the disparity increases with age. The origin and magnitude of this effect are considered below, firstly for an idealized, theoretical ²¹°Pb profile and secondly for a freshwater lake sediment core. A brief consideration is presented of the implications of this potential artefact for sampling and analysis.

Chitosan as a potential amendment to remediate metal contaminated soil - a characterisation study.

The potential of chitosan, a fishery waste-based material, as a soil amendment to clean-up metal contaminated soil was investigated. Chitosan was treated using glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) as cross-linking reagents to enhance its chemical stability in acidic media and to improve its physical properties. Cross-linking treatment had significant effects on chitosan surface area, pore diameter, surface morphology and crystallinity. Interaction with Ag(I), Pb(II) and Cu(II) decreased the crystallinity of the materials and changed their surface morphology significantly. FTIR analysis confirmed that N and O atoms served as binding sites for the metal ions. Chitosan and treated chitosans were able to bind metal ions, even in the presence of K(+), Cl(-) and NO(3)(-), which are dominant ions in soil. Therefore, remediation of metal contaminated soil using chitosan and cross-linked treated chitosans as soil amendments is feasible.

Microbial respiration as an indication of metal toxicity in contaminated organic materials and soil.

The effect of heavy metals on microbial respiration in organic materials used as soil amendments was evaluated to assess the stability of the materials. Solutions of Pb (II), Cu (II) and Zn (II) at rates of 5, 10 and 50mg metal g(-1) were added to green waste compost, peat, coir and wood bark. Metal toxicity led to a significant decrease in carbon dioxide evolved by the contaminated materials, up to 80% less at the highest rate of addition compared to the untreated material. There was a significant negative correlation between the organic carbon content of an amendment and the inhibition of CO(2) evolution by all three heavy metals. There was also a significant negative correlation between an amendment's cation exchange capacity and the inhibition of CO(2) evolution caused by Cu and Zn. The ability of the organic materials to enhance respiration in a soil from the vicinity of a Pb/Zn mine was also evaluated, by applying them to the soil at rates of 1, 10 and 20%. CO(2) evolution from the contaminated soil was enhanced significantly by the addition of all of the amendments, with coir causing up to 90% enhancement at high levels of addition.

Carbon deposition and phase transformations in red mud on exposure to methane.

A characterization study detailing the phase transformations and microstructural nature of the carbon deposited during methane decomposition over red mud has been undertaken. In situ XRD was carried out to study the phase transformation sequences of red mud during the reaction. Scanning electron microscopy, high resolution transmission electron microscopy, thermogravimetric analysis, BET surface area determination and CHN analysis were carried out to investigate the properties of the post-reaction samples. Exposure to methane with increasing temperature caused a stepwise reduction of iron oxides in red mud and promoted methane cracking leading to carbon deposition. The presence of carbon nanostructures was confirmed by HRTEM observations. The carbon formed was graphitic in nature and the spent red mud, rich in Fe and Fe(3)C formed as a result of the reduction of the iron oxide, was magnetic in nature. The surface area of the material was enhanced upon reaction. In addition, reactivity comparisons between goethite and red mud were carried out to study the formation of carbon oxides during reaction.

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations.

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.

Sorption of Cu and Zn by bone charcoal.

Bone charcoal is being developed as a treatment for decontaminating polluted water. In particular, its potential to adsorb metal species from contaminated water supplies is being examined. In this study, bone charcoal was used in batch and column experiments designed to investigate the sorption of two cationic metals Cu and Zn. The data from batch experiments fitted the Langmuir isotherm and so theoretical maximum binding capacities could be obtained. These values were compared with experimental values derived from the column experiments. The mechanisms involved in the immobilisation were also investigated.

Phytoremediation of heavy metal-contaminated land by trees--a review.

This paper reviews the potential for using trees for the phytoremediation of heavy metal-contaminated land. It considers the following aspects: metal tolerance in trees, heavy metal uptake by trees grown on contaminated substrates, heavy metal compartmentalisation within trees, phytoremediation using trees and the phytoremediation potential of willow (Salix spp.).

Development of a hydroponic screening technique to assess heavy metal resistance in willow (Salix).

A nutrient thin film hydroponic system has been developed which allows rapid screening of willow (Salix) clones for their resistance to heavy metals, and hence their use in phytoremediation. Two clones known to be different in their resistance to heavy metals (Salix burjatica (Germany) and S. triandra x viminalis (Q83)), could be distinguished on the basis of leaf biomass, root biomass and stem height after 6 weeks. There were also differences in the uptake of heavy metals between the two clones.

Screening of willow species for resistance to heavy metals: comparison of performance in a hydroponics system and field trials.

The aim of this study was to ascertain whether metal resistance in willow (Salix) clones grown in a hydroponics screening test correlated with data from the same clones grown independently in a field trial. If so, results from a short-term, glasshouse-based system could be extrapolated to the field, allowing rapid identification of willows suitable for planting in metal-contaminated substrates without necessitating longterm field trials. Principal Components Analysis was used to show groups of clones and to assess the relative importance of the parameters measured in both the hydroponics system and the field; including plant response factors such as increase in stem height, as well as metal concentrations in plant tissues. The clones tested fell into two distinct groups. Salix viminalis clones and the basket willow Black Maul (S. triandra) were less resistant to elevated concentrations of heavy metals than a group of hardier clones, including S. burjatica 'Germany,' S.x dasyclados, S. candida and S. spaethii. The more resistant clones produced more biomass in the glasshouse and field, and had higher metal concentrations in the wood. The less resistant clones had greater concentrations of Cu and Ni in the bark, and produced less biomass in the glasshouse and field. Significant relationships were found between the response of the same clones grown the in short-term glasshouse hydroponics system and in the field.

Tissue nutrient signatures predict herbaceous-wetland community responses to nutrient availability.

• An extensive survey of European wetlands was undertaken to compare the importance of growing conditions vs functional characteristics of vegetation in determining N, P and K contents. • Stress-tolerator dominated stands (S) had consistently lower nutrient contents and higher N : P ratios whereas ruderal-dominated (R) stands displayed the opposite pattern. Competitor (C) and competitor-stress tolerator (CS) stands were intermediate to R and S. • These patterns were mostly preserved after removing covariation between vegetation and environment, thus indicating constitutional differences in nutrient signatures between functionally differentiated vegetation. C and R stands were least likely to be nutrient limited. Half of the S stands were probably P-limited but C, CS and R stands rarely or never experienced P limitation. Inferred colimitation by K was twice as frequent in S stands compared with other vegetation. • This study extends the evidence for syndromes of traits closely linked to nutrient use efficiency that increase fitness under particular growing conditions. It also highlights patterns at a community level across a wide range of wetland types and suggests that tissue nutrient signatures will have diagnostic value in predicting community responses to perturbation in nutrient availability.