Transfer of polychlorinated, polybrominated and mixed-halogenated dioxins, furans and biphenyls, polychlorinated naphthalenes and alkanes, polycyclic aromatic hydrocarbons and chlorobenzenes to the milk of dairy cattle from controlled ingestion of industrial and municipal bioresources recycled to agricultural land.

Recycled bioresources (biosolids, compost-like-output, meat and bonemeal ash, poultry litter ash, paper sludge ash) were added to the feed of dairy cattle to simulate incidental ingestion from agricultural utilisation, to investigate the transfer of organic contaminants from the ingested materials to milk. The bioresources were blended with a loamy sand soil at agronomic rates to simulate a single application to land, which was added to the diet at 5 % of the total intake on a dry matter (DM) basis. Biosolids, and control treatments consisting of unamended soil, were also added directly to the feed at 5 % DM. The cattle were fed the bioresource amended diets for a target period of three to four weeks, depending on material, and monitoring continued for four weeks after treatment withdrawal. Milk samples were taken weekly with chemical analysis of selected samples for a range of organic contaminants including: polychlorinated, polybrominated and mixed-halogenated dioxins, furans and biphenyls, polychlorinated naphthalenes and alkanes (often called chlorinated paraffins), polycyclic aromatic hydrocarbons and chlorobenzenes. No statistically significant additional transfer of organic contaminants to the milk was detected due to the relatively low levels of contaminants present when the bioresources were incorporated with soil at agronomic rates. However, direct biosolids ingestion by cattle significantly increased the transfer of contaminants to milk in comparison to control animals. Although present in larger concentrations in biosolids than their chlorinated counterparts, the carry over rates and bioconcentration factors of brominated dioxins and furans were considerably smaller. Direct ingestion of biosolids resulted in most contaminants approaching, but not always completely reaching, steady state concentrations within the treatment feeding period, however, concentrations generally declined to control values within four-weeks after withdrawing the biosolids-amended diet.

Concentrations of organic contaminants in industrial and municipal bioresources recycled in agriculture in the UK.

Many types of bioresource materials are beneficially recycled in agriculture for soil improvement and as alternative bedding materials for livestock, but they also potentially transfer contaminants into plant and animal foods. Representative types of industrial and municipal bioresources were selected to assess the extent of organic chemical contamination, including: (i) land applied materials: treated sewage sludge (biosolids), meat and bone meal ash (MBMA), poultry litter ash (PLA), paper sludge ash (PSA) and compost-like-output (CLO), and (ii) bedding materials: recycled waste wood (RWW), dried paper sludge (DPS), paper sludge ash (PSA) and shredded cardboard. The materials generally contained lower concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (PCBs) relative to earlier reports, indicating the decline in environmental emissions of these established contaminants. However, concentrations of polycyclic aromatic hydrocarbons (PAHs) remain elevated in biosolids samples from urban catchments. Polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) were present in larger amounts in biosolids and CLO compared to their chlorinated counterparts and hence are of potentially greater significance in contemporary materials. The presence of non-ortho-polychlorinated biphenyls (PCBs) in DPS was probably due to non-legacy sources of PCBs in paper production. Flame retardent chemicals were one of the most significant and extensive groups of contaminants found in the bioresource materials. Decabromodiphenylether (deca-BDE) was the most abundant polybrominated diphenyl ether (PBDE) and may explain the formation and high concentrations of PBDD/Fs detected. Emerging flame retardant compounds, including: decabromodiphenylethane (DBDPE) and organophosphate flame retardants (OPFRs), were also detected in several of the materials. The profile of perfluoroalkyl substances (PFAS) depended on the type of waste category; perfluoroundecanoic acid (PFUnDA) was the most significant PFAS for DPS, whereas perfluorooctane sulfonate (PFOS) was dominant in biosolids and CLO. The concentrations of polychlorinated alkanes (PCAs) and di-2-ethylhexyl phthalate (DEHP) were generally much larger than the other contaminants measured, indicating that there are major anthropogenic sources of these potentially hazardous chemicals entering the environment. The study results suggest that continued vigilance is required to control emissions and sources of these contaminants to support the beneficial use of secondary bioresource materials.

Novel integrated mechanical biological chemical treatment (MBCT) systems for the production of levulinic acid from fraction of municipal solid waste: A comprehensive techno-economic analysis.

This paper, for the first time, reports integrated conceptual MBCT/biorefinery systems for unlocking the value of organics in municipal solid waste (MSW) through the production of levulinic acid (LA by 5wt%) that increases the economic margin by 110-150%. After mechanical separation recovering recyclables, metals (iron, aluminium, copper) and refuse derived fuel (RDF), lignocelluloses from remaining MSW are extracted by supercritical-water for chemical valorisation, comprising hydrolysis in 2wt% dilute H2SO4 catalyst producing LA, furfural, formic acid (FA), via C5/C6 sugar extraction, in plug flow (210-230°C, 25bar, 12s) and continuous stirred tank (195-215°C, 14bar, 20min) reactors; char separation and LA extraction/purification by methyl isobutyl ketone solvent; acid/solvent and by-product recovery. The by-product and pulping effluents are anaerobically digested into biogas and fertiliser. Produced biogas (6.4MWh/t), RDF (5.4MWh/t), char (4.5MWh/t) are combusted, heat recovered into steam generation in boiler (efficiency: 80%); on-site heat/steam demand is met; balance of steam is expanded into electricity in steam turbines (efficiency: 35%).

Heavy metal leaching and environmental risk from the use of compost-like output as an energy crop growth substrate.

Conversion of productive agricultural land towards growth of energy crops has become increasingly controversial. Closed landfill sites represent significant areas of brownfield land, which have potential for the establishment of energy crops. Increasingly composts are now being produced from the degradable fraction of mixed municipal solid waste (MSW) and are commonly referred to as Compost-Like-Output (CLO). However, leaching of heavy metal and other elements due to the use of CLO as soil amendment has the potential to pose a risk to the wider environment as a diffuse pollution source if not managed correctly. Salix viminalis and Eucalyptus nitens were grown at 5 different CLO application rates (equivalent to 250, 1000, 3000, 6000, 1,0000 kg N/Ha) with weekly leachate analysis to assess the solubility of heavy metals and the potential release into the environment. The change in plant total dry mass suggested 3,000 kgN/Ha as the optimum application rate for both species. Weekly leachate analysis identified excess soluble ions within the first 4 weeks, with heavy metals concentrations exceeding water quality limits at the higher application rates (>3,000 kg N/Ha). Heavy metal uptake and accumulation within each species was also investigated; S. viminalis accumulated greater levels of heavy metals than E. nitens with a general trend of metal accumulation in root>stem>leaf material. Heavy metal leaching from soils amended with CLO has the potential to occur at neutral and slightly alkaline pH levels as a result of the high buffering capacity of CLO. The use of CLO at application rates of greater than 250 kg N/Ha may be limited to sites with leachate collection and containment systems, not solely for the heavy metal leaching but also excess nitrogen leaching. Alternatively lower application rates are required but will also limit biomass production.