Re-use of agricultural wastes for the removal and recovery of Zr(IV) from aqueous solutions

This study assesses the feasibility of Zr(IV) removal and recovery from aqueous solutions by novel biosorbents prepared from selected agricultural wastes. Sugarcane bagasse was selected for further investigation after showing increased biosorption capacity during the initial screening experiment. The biosorption efficiency of native (untreated), SDS-treated and immobilised bagasse for Zr(IV) removal was studied and optimization of the experimental conditions carried out including pH, biosorbent weight, contact time, initial metal ion concentration and temperature to maximise adsorption. Sorbent–sorbate reaction behaviour was estimated by fitting equilibrium data by non-linear and transformed linear forms of the Langmuir, Freundlich and Redlich–Peterson isotherms as well as pseudo-first and second-order kinetic models. The best fitting isothermal or kinetic model was optimized by comparing linear and non-linear R2 value and non-linear regression error functions. H2SO4 proved to be the most effective desorbing agent in recovery of the sorbed Zr(IV) ions from all forms of bagasse. Biosorbent characterisation and effectiveness of the process was confirmed by Fourier transform infra-red spectroscopy (FT-IR), scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDX). The data illustrate that native (untreated), SDS-treated and immobilised bagasse have great potential to remove and recover Zr from wastewater

Mobility of antimony, arsenic and lead at a former mine, Glendinning, Scotland

Elevated concentrations of antimony (Sb), arsenic (As) and lead (Pb) in upland organic-rich soils have resulted from past Sb mining activities at Glendinning, southern Scotland. Transfer of these elements into soil porewaters was linked to the production and leaching of dissolved organic matter and to leaching of spoil material. Sb was predominantly present in truly dissolved (< 3 kDa) forms whilst As and Pb were more commonly associated with large Fe-rich/organic colloids. The distinctive porewater behaviour of Sb accounts for its loss from deeper sections of certain cores and its transport over greater distances down steeper sections of the catchment. Although Sb and As concentrations decreased with increasing distance down a steep gully from the main spoil heap, elevated concentrations (~ 6-8 and 13-20 μg L− 1, respectively) were detected in receiving streamwaters. Thus, only partial attenuation occurs in steeply sloping sections of mining-impacted upland organic-rich soils and so spoil-derived contamination of surface waters may continue over time periods of decades to centuries

Strategies for producing biochars with minimum PAH contamination

With the aim to develop initial recommendations for production of biochars with minimal contamination with polycyclic aromatic hydrocarbons (PAHs), we analysed a systematic set of 46 biochars produced under highly controlled pyrolysis conditions. The effects of the highest treatment temperature (HTT), residence time, carrier gas flow and typical feedstocks (wheat / oilseed rape straw pellets (WSP), softwood pellets (SWP)) on 16 US EPA PAH concentration in biochar were investigated. Overall, the PAH concentrations ranged between 1.2 and 100 mg kg-1. On average, straw-derived biochar contained 5.8 times higher PAH concentrations than softwood-derived biochar. In a batch pyrolysis reactor, increasing carrier gas flow significantly decreased PAH concentrations in biochar; in case of straw, the concentrations dropped from 43.1 mg kg-1 in the absence of carrier gas to 3.5 mg kg-1 with a carrier gas flow of 0.67 L min-1; for woody biomass PAHs concentrations declined from 7.4 mg kg-1 to 1.5 mg kg-1 with the same change of carrier gas flow. In the temperature range of 350-650°C the HTT did not have any significant effect on PAH content in biochars, irrespective of feedstock type, however, in biochars produced at 750°C the PAH concentrations were significantly higher. After detailed investigation it was deduced that this intensification in PAH contamination at high temperatures was most likely down to the specifics of the unit design of the continuous pyrolysis reactor used. Overall, it was concluded that besides PAH formation, vaporisation is determining the PAH concentration in biochar. The fact that both of these mechanisms intensify with pyrolysis temperature (one increasing and the other one decreasing the PAH concentration in biochar) could explain why no consistent trend in PAH content in biochar with temperature has been found in the literature

Persistence of chlorpropham (CIPC) in the concrete flooring of potato stores

The loss of the sprout suppressant, chlorpropham (CIPC), to the fabric of potato stores is currently of concern due to the risk of potential cross contamination of other crops subsequently housed in these stores. HPLC UV/VIS and GCMS methods were successfully employed to detect CIPC in the concrete flooring of research and commercial potato stores with histories of between 1 and 26 years of use. The concentrations in identical research stores, with different numbers of applications, were in the range 0.58–5.7 and 3.4–112 μg g−1, suggesting the magnitude of contamination was influenced by the number of applications. Commercial store A, with a history of 18 seasons of applications (estimate of total CIPC applied 2040 kg), had concentrations varying between 6 and 48 μg g−1 in the top three centimetres, with more than 92% within the top centimetre. In contrast, commercial store B, with a history of less than five seasons of applications (estimate of total CIPC applied 319 kg), had concentrations varying between 0.58 and 304 μg g−1 in the top four centimetres, with less than 47% within the top centimetre. The difference in depth distributions between A and B may be due to the structural integrity of the concrete, which was much poorer in B. CIPC was persistent in all stores irrespective of the total quantities of CIPC applied and date of the final application

Strategies for producing biochars with minimum PAH contamination

With the aim to develop initial recommendations for production of biochars with minimal contamination with polycyclic aromatic hydrocarbons (PAHs), we analysed a systematic set of 46 biochars produced under highly controlled pyrolysis conditions. The effects of the highest treatment temperature (HTT), residence time, carrier gas flow and typical feedstocks (wheat / oilseed rape straw pellets (WSP), softwood pellets (SWP)) on 16 US EPA PAH concentration in biochar were investigated. Overall, the PAH concentrations ranged between 1.2 and 100 mg kg-1. On average, straw-derived biochar contained 5.8 times higher PAH concentrations than softwood-derived biochar. In a batch pyrolysis reactor, increasing carrier gas flow significantly decreased PAH concentrations in biochar; in case of straw, the concentrations dropped from 43.1 mg kg-1 in the absence of carrier gas to 3.5 mg kg-1 with a carrier gas flow of 0.67 L min-1; for woody biomass PAHs concentrations declined from 7.4 mg kg-1 to 1.5 mg kg-1 with the same change of carrier gas flow. In the temperature range of 350-650°C the HTT did not have any significant effect on PAH content in biochars, irrespective of feedstock type, however, in biochars produced at 750°C the PAH concentrations were significantly higher. After detailed investigation it was deduced that this intensification in PAH contamination at high temperatures was most likely down to the specifics of the unit design of the continuous pyrolysis reactor used. Overall, it was concluded that besides PAH formation, vaporisation is determining the PAH concentration in biochar. The fact that both of these mechanisms intensify with pyrolysis temperature (one increasing and the other one decreasing the PAH concentration in biochar) could explain why no consistent trend in PAH content in biochar with temperature has been found in the literature

Accumulation of Sellafield-derived radiocarbon (14C) in Irish Sea and West of Scotland intertidal shells and sediments

The nuclear energy industry produces radioactive waste at various stages of the fuel cycle. In the United Kingdom, spent fuel is reprocessed at the Sellafield facility in Cumbria on the north west coast of England. Waste generated at the site comprises a wide range of radionuclides including radiocarbon (14C) which is disposed of in various forms including highly soluble inorganic carbon within the low level liquid radioactive effluent, via pipelines into the Irish Sea. This 14C is rapidly incorporated into the dissolved inorganic carbon (DIC) reservoir and marine calcifying organisms, e.g. molluscs, readily utilise DIC for shell formation. This study investigated a number of sites located in Irish Sea and West of Scotland intertidal zones. Results indicate 14C enrichment above ambient background levels in shell material at least as far as Port Appin, 265 km north of Sellafield. Of the commonly found species (blue mussel (Mytilus edulis), common cockle (Cerastoderma edule) and common periwinkle (Littorina littorea)), mussels were found to be the most highly enriched in 14C due to the surface environment they inhabit and their feeding behaviour. Whole mussel shell activities appear to have been decreasing in response to reduced discharge activities since the early 2000s but in contrast, there is evidence of continuing enrichment of the carbonate sediment component due to in-situ shell erosion, as well as indications of particle transport of fine 14C-enriched material close to Sellafield

Ecosystem uptake and transfer of Sellafield-derived radiocarbon (14C). Part 1. The Irish Sea

Ecosystem uptake and transfer processes of Sellafield-derived radiocarbon (14C) within the Irish Sea were examined. Highly variable activities in sediment, seawater and biota indicate complex 14C dispersal and uptake dynamics. All east basin biota exhibited 14C enrichments above ambient background while most west basin biota had 14C activities close to background, although four organisms including two slow-moving species were significantly enriched. The western Irish Sea gyre is a suggested pathway for transfer of 14C to the west basin and retention therein. Despite ongoing Sellafield 14C discharges, organic sediments near Sellafield were significantly less enriched than associated benthic organisms. Rapid scavenging of labile, 14C-enriched organic material by organisms and mixing to depth of 14C-enriched detritus arriving at the sediment/water interface are proposed mechanisms to explain this. All commercially important fish, crustaceans and molluscs showed 14C enrichments above background; however, the radiation dose from their consumption is extremely low and radiologically insignificant

Determination of Chlorpropham (CIPC) residues, in the concrete flooring of potato stores, using quantitative (HPLC UV/VIS) and qualitative (GCMS) methods

Isopropyl-N-(3-chlorophenyl) carbamate (CIPC, common name Chlorpropham) is commonly used for post-harvest sprout inhibition in stored potatoes. It is applied as a thermal fog which results in loss to the fabric of the store and the atmosphere. Recently, there have been concerns in the United Kingdom because of cross contamination of other crop commodities that were stored in buildings with a history of CIPC usage. This cross contamination may have occurred because of retained residues in the fabric of the stores. The retention of CIPC in concrete is poorly understood; therefore the requirement for a robust analytical method for the detection and quantification of CIPC in concrete is a critical first step in tackling this problem. A method using High-Performance Liquid Chromatography with ultraviolet detection (HPLC UV/VIS) was validated. CIPC recoveries at three concentration levels (0.4, 4.0 and 40.0 µg g-1) were in the range of 90.7-97.0 % with relative standard deviations between 2.14-3.01 %. The limits of detection and quantification were 0.03 and 0.1 µg g-1 , respectively. This study confirmed that CIPC was persistent in concrete to a depth of 4 cm, with > 90 % within the top 1 cm of the flooring

The risk of chlorpropham cross-contamination of grain in potato stores

The contamination of food with pesticide residues is of significant concern to consumers and legislation has been implemented worldwide to ensure compliance with Maximum Residue Levels of chemicals in food. The occurrence of the potato sprout inhibitor, isopropyl N-(3-chlorophenyl) carbamate (chlorpropham or CIPC) residues on cereals, such as wheat, is of concern as this chemical is not authorised for use on cereals, and therefore the route of unintentional contamination warrants further investigation. This study reports on the risk of CIPC cross-contamination of grain that was stored in a commercial potato store and provides a method for low level quantification of CIPC in cereals. A High Performance Liquid Chromatography (HPLC UV/VIS) method for quantifying residues of CIPC in grains was successfully validated and the presence of CIPC was confirmed by Gas Chromatography Mass Spectrometry (GCMS). The magnitude of contamination in the grain was influenced by: (I) direct contact with the flooring of the store; (II) the headspace directly above the concrete surface and within the store itself and (III) contaminated dust/CIPC particles in the store atmosphere. Cross contamination is feasible irrespective of the CIPC concentrations in the concrete flooring and even with storage of grain at an elevated height above the concrete, suggesting that the route of cross contamination is a complex process involving physical and chemical (volatilization) factors. The results are significant for recommendations involving the storage of grain in buildings with a history of CIPC use and for remedial strategies for decontamination of these buildings

A green approach for the removal of Sr(II) from aqueous media: kinetics, isotherms and thermodynamic studies

Adsorption efficiency of native, NaOH-treated and immobilized peanut husk and sugarcane bagasse for Sr(II) removal was studied in batch mode. In view of promising adsorption efficiency of peanut husk versus sugarcane bagasse, the biosorption behaviour of the Sr(II) ions onto peanut husk (native and modified) was studied as a function of pH, biosorbent dose, contact time, initial metal ion concentration and temperature for the maximum removal of Sr(II) ions. Linear and non-linear pseudo-first and second-order kinetic models were applied and value of R2 and six non-linear regression error functions, namely hybrid fractional error function (HYBRID), Marquardt's percent standard deviation (MPSD), average relative error (ARE), the sum of the errors squared (ERRSQ/SSE), the sum of the absolute errors (EABS) and Chi-square test (χ2) were used to predict the most optimum kinetic model. Sorbent-sorbate reaction nature was estimated by fitting equilibrium data by non-linear and transformed linear forms of the Langmuir, Freundlich and Redlich-Peterson isotherms and most optimum isothermal model was optimized by comparing linear and non-linear R2 value and non-linear regression error functions. HCl proved most successful eluating agents for sorbed Sr(II) ions. Biosorption characteristics and effectiveness of the process was also confirmed by Fourier transform infra-red spectroscopy (FTIR), scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDX). In view of promising efficiency of peanut husk as an adsorbent, it could possibly be used for the removal of Sr(II) ions from aqueous medium and is also extendable to other radionuclide