Recovery and re-use of phosphorus (P) from wastewater treatment systems as agricultural fertiliser presents an important and viable target for P waste reduction and recycling. In this study novel biochar materials for P filtration of wastewater were designed and produced using waste feedstocks, with consideration of the plant accessibility of the P captured by the biochars. The biochars were produced using batch slow pyrolysis at 450 °C and 550 °C from a) AD: anaerobically digested sewage sludge and b) OCAD: a 1:1 mixture of anaerobically digested sewage sludge and ochre, a mineral product from mine drainage treatment. A set of experiments was designed using pH buffering to provide a robust framework for assessing the P recovery capacity and affinity of the biochars compared to other potential P recovery materials (unprocessed ochre, activated carbon and zeolite). After 5 days of repeated exposure to a P solution at a wastewater-relevant concentration (0.02 g P l(-1)) replenished each 24 h, relatively high masses of P were recovered by ochre (1.73 ± 8.93×10(-3) mg P g(-1)) and the biochars OCAD550 (1.26 ± 4.66×10(-3) mg P g(-1)), OCAD450 (1.24 ± 2.10×10(-3) mg P g(-1)), AD450 (1.06 ± 3.84×10(-3) mg P g(-1)), and AD550 (0.986 ± 9.31×10(-3) mg P g(-1)). The biochar materials had higher removal rates than both activated carbon (0.884 ± 1.69×10(-2) mg P g(-1)) and zeolite (0.130 ± 1.05×10(-2) mg P g(-1)). To assess the extractability of recovered P, P exposure was followed by repeated extraction for 4 days with pH 7-buffered deionised water. The AD biochars retained 55% of the P recovered, OCAD biochars 78% and ochre 100%. Assessment of potentially toxic element concentrations in the biochars against guideline values indicated low risk associated with their use in the environment. Our successful demonstration of biochar materials highlights the potential for further development of P filters for wastewater treatment systems from anaerobic digestate produced and pyrolysed on-site with energy recovery.
This review focuses on the applicability of red mud as an amendment for metal/metalloid-contaminated soil. The varying properties of red muds from different sources are presented as they influence the potentially toxic element (PTE) concentration in amended soil. Experiments conducted worldwide from the laboratory to the field scale are screened and the influencing parameters and processes in soils are highlighted. Overall red mud amendment is likely to contribute to lowering the PTE availability in contaminated soil. This is attributed to the high pH, Fe and Al oxide/oxyhydroxide content of red mud, especially hematite, boehmite, gibbsite and cancrinite phases involved in immobilising metals/metalloids. In most cases red mud amendment resulted in a lowering of metal concentrations in plants. Bacterial activity was intensified in red mud-amended contaminated soil, suggesting the toxicity from PTEs was reduced by red mud, as well as indirect effects due to changes in soil properties. Besides positive effects of red mud amendment, negative effects may also appear (e.g. increased mobility of As, Cu) which require site-specific risk assessments. Red mud remediation of metal/metalloid contaminated sites has the potential benefit of reducing red mud storage and associated problems.
Treatment of polluting discharges from abandoned coal mines in the UK currently produces ca 30,000 t y(-1) of hydrous iron oxides ("ochre"), for which there is no major end-use, but which has previously been shown to have potential for removing P from wastewater and agricultural runoff. The efficiency of ochre for P removal from wastewater was investigated in experiments at two sites in the UK: Leitholm in Scotland and Windlestone in England. The three-year experiment at Leitholm involved diverting secondary-treated wastewater effluent through a trough which contained granular and pelletized ochre at different times. In the nine-month experiment at Windlestone, beds of ochre pellets in horizontal and vertical flow configurations were tested. The ochre treatment systems at Leitholm reduced influent concentrations of total P (TP) and TP mass by ca 80% and 50%, respectively, during optimal flow conditions, and achieved a removal rate of up to 65+/-48 mg TP kg(-1) ochre d(-1). There was no detectable release of potentially toxic metals from the ochre during the experiments. P removal rates by concentration were inversely related to flow and declined during the different phases of the experiments, probably due to clogging. At Windlestone, higher removal rates up to 195 mg TP kg(-1) ochre d(-1) were achieved for short periods of time following cleaning of the experimental system. Ochre has considerable potential to remove P from wastewater in a multi-stage treatment system and has a lifetime estimated to be 10 times longer than other substrates tested for P removal.
[1] Methyl bromide (CH 3 Br) is a trace gas involved in stratospheric ozone depletion with both anthropogenic and natural sources. Estimates of natural source strengths are highly uncertain. In this study, >320 highly temporally and spatially resolved measurements of CH 3 Br emissions from a salt marsh in Scotland (56°00 0 N, 2°35 0 W) were made during one year using eight static enclosures. Net emissions showed both strong seasonal and diurnal cycles. Day-today maxima in emissions were associated with sunny days. Emissions dropped to zero when vegetation was removed. Mean measured CH 3 Br emission was 350 ng m À2 h À1 , but a few ''hot spots'' (measured maximum 4000 ng m À2 h À1 ) dominated integrated emissions. A crude scale-up of the annual mean emission yields an estimate for global CH 3 Br emission of $1 (0.5-3) Gg y À1 (range uses annual mean from lowest and highest emitting enclosures), $10% the global salt marsh emission regularly quoted in the literature.
Depletion of soil nutrients is a major cause of decline in productivity of forest plantations in successive rotations. Biochar amendment in agricultural systems has been shown to yield various beneficial effects, including increasing soil phosphorus (P) availability. However, the direct and indirect effects of biochar addition on forest soil P dynamics have largely been unexplored. The objective of this study was to examine how biochar produced from harvest residue (leaves and woodchips) affect the P dynamics in second rotation Cunninghamia lanceolata (Chinese fir) plantation soil. An incubation experiment which involved mixing of forest soil with 1% or 3% w/w leaf or woodchip biochar, pyrolyzed at 300 °C or 600 °C, was conducted for 80 days at 20 °C. After 7, 40 and 80 days of incubation, soil samples were analyzed for total and available P, inorganic and organic P pools, and soil phosphatase activity. At the end of the incubation period, bacterial community composition and diversity were analyzed by 16S rDNA sequencing. The leaf biochar produced at both pyrolysis temperatures was more alkaline and had significantly higher soluble P, nitrogen and calcium contents than the woodchip biochar. Soil total and available P increased significantly in all leaf biochar treatments after 80 days incubation compared to the untreated control soil, but the woodchip biochar treatments had no significant effects.
No single end-use has yet been identified that is capable of consuming the projected production of ochre (mainly iron (III) oxides) from mine drainage treatment. However, the high sorption capacity of ochre for phosphorus (up to 26 mg kg(-1)) means that it could be used in constructed wetlands to enhance phosphorus removal. Laboratory batch experiments showed that coarse-grained ochre removes 90% of all phosphorus forms from sewage effluent after 15 minutes of shaking. From a larger-scale experiment, it is estimated that constructed wetlands with an ochre substrate should remove phosphorus from sewage effluent for up to 200-300 years. The suitability of ochre for phosphorus removal is being investigated at the field scale in a wastewater constructed wetland (175 m2 area) in Berwickshire, UK. The hydraulic and treatment performance of the wetland were monitored for 15 months prior to installation at the inlet in November 2003 of a tank containing approximately 1200 kg ochre. Results so far show that improved hydraulic design is required for ochre to increase the mean phosphorus removal efficiency of the system (27 +/- 28%), but potentially toxic metals (Al, Cd, Cr, Cu, Fe, Ni, Pb, Zn) have not been released from the ochre into the wetland outflow.
Since removal and disposal of sustainable urban drainage system (SUDS) sediment can incur high maintenance costs, assessments of sediment volumes, quality and frequency of removal are required. Sediment depth and quality were surveyed annually from 1999-2003 in three ponds and one wetland in Dunfermline, Scotland, UK. Highest sediment accumulation occurred in Halbeath Pond, in the most developed watershed and with no surface water management train. From comparison of measured potentially toxic metal concentrations (Cd, Cr, Cu, Fe, Ni, Pb, Zn) with standards, the average sediment quality should not impair aquatic ecosystems. 72-84% of the metal flux into the SUDS was estimated to be associated with coarse sediment (> 500 microm diameter) suggesting that management of coarse sediment is particularly important at this site. The timing of sediment removal for these SUDS is expected to be determined by loss of storage volume, rather than by accumulation of contaminants. If sediment removal occurs when 25% of the SUDS storage volume has infilled, it would be required after 17 years in Halbeath Pond, but only after 98 years in Linburn Pond (which has upstream detention basins). From the quality measurements, sediment disposal should be acceptable on adjacent land within the boundaries of the SUDS studied.
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