Driving forces and barriers in the removal of phosphorus from water using crop residue, wood and sewage sludge derived biochars.

The removal of phosphorus (P) from sewage effluents is necessary to control eutrophication in receiving waters. Biochar has been proposed and is investigated for the capture and reuse of P, however the forces driving and limiting P adsorption are still largely unclear. To identify the forces governing P uptake by biochar, biochars with markedly different physicochemical characteristics derived from a variety of biomass (oilseed rape straw, wheat straw, miscanthus straw, rice husk, soft wood and sewage sludge residue), pyrolysed at various temperatures, were investigated. The biochar samples were characterised in terms of pH, electrical conductivity, total acidity, carbon chemistry, metal composition, surface area, and porosity, and the uptake and release of P was compared to the biochar properties using multivariate analysis. Uptake of P by the biochars as such was low (< 0.71 mg P/g biochar with feed solutions of 50 mg P/l) and, among the variables studied, the biochars' Ca and Mg content was key in P removal and found to be pH dependant. Enhancement of biochar surface area and porosity was carried out by activation with CO2 at 800 °C and the uptake significantly improved (p < 0.05) (i.e. an increased surface area from <20 m2/g up to 781 m2/g gave a limited improvement in P removal to <1.2 mg P/g biochar at feed level of 50 mg P/l). These results confirm that the potential to use these unmodified biochars derived from a variety of biomass for P sorption is low, but that the material provides properties that may be modified or enhanced to increase sorption capacity. This study indicates that biochar/biochar feedstock with greater content of Ca and Mg will be more advantageous for P capture.

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 <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 <1 mg P/L.

Opportunities and challenges in the use of coal fly ash for soil improvements--a review.

Coal fly ash (CFA), a by-product of coal combustion has been regarded as a problematic solid waste, mainly due to its potentially toxic trace elements, PTEs (e.g. Cd, Cr, Ni, Pb) and organic compounds (e.g. PCBs, PAHs) content. However, CFA is a useful source of essential plant nutrients (e.g. Ca, Mg, K, P, S, B, Fe, Cu and Zn). Uncontrolled land disposal of CFA is likely to cause undesirable changes in soil conditions, including contamination with PTEs, PAHs and PCBs. Prudent CFA land application offers considerable opportunities, particularly for nutrient supplementation, pH correction and ameliorating soil physical conditions (soil compaction, water retention and drainage). Since CFA contains little or no N and organic carbon, and CFA-borne P is not readily plant available, a mixture of CFA and manure or sewage sludge (SS) is better suited than CFA alone. Additionally, land application of such a mixture can mitigate the mobility of SS-borne PTEs, which is known to increase following cessation of SS application. Research analysis further shows that application of alkaline CFA with or without other amendments can help remediate at least marginally metal contaminated soils by immobilisation of mobile metal forms. CFA land application with SS or other source of organic carbon, N and P can help effectively reclaim/restore mining-affected lands. Given the variability in the nature and composition of CFA (pH, macro- and micro-nutrients) and that of soil (pH, texture and fertility), the choice of CFA (acidic or alkaline and its application rate) needs to consider the properties and problems of the soil. CFA can also be used as a low cost sorbent for the removal of organic and inorganic contaminants from wastewater streams; the disposal of spent CFA however can pose further challenges. Problems in CFA use as a soil amendment occur when it results in undesirable change in soil pH, imbalance in nutrient supply, boron toxicity in plants, excess supply of sulphate and PTEs. These problems, however, are usually associated with excess or inappropriate CFA applications. The levels of PAHs and PCBs in CFA are generally low; their effects on soil biota, uptake by plants and soil persistence, however, need to be assessed. In spite of this, co-application of CFA with manure or SS to land enhances its effectiveness in soil improvements.

Phosphorus species and fractionation--why sewage derived phosphorus is a problem.

Phosphorus (P) inputs to sewage treatment works (STW) come from a variety of sources and filtration of treated wastewater prior to discharge into receiving waters is a common practice. This means P in treated wastewaters may be present in forms that are potentially more bioavailable and mobile. We conducted a 2-year study to determine P species up and downstream of two STW outfalls into two tributaries of the River Thames. Downstream of the outfalls, P concentrations in both rivers were frequently greater by an order of magnitude for all species of P. A high proportion of total P (TP) in the downstream waters was determined as dissolved, which was largely comprised of soluble reactive P (SRP) - considered as the most bioavailable P species. Furthermore no significant difference in SRP was found in receiving waters passed through 0.45 and 0.10 µm filters. This means that P from STWs occurs in <0.1 µm fraction size, which will not readily settle to the channel bed and is more easily assimilated by biota. This distinguishes STW inputs from agricultural runoff where a high proportion of P occurs as particulate P which is both less bioavailable and more likely to settle to the channel bed. This implies that STWs derived P is likely to have a greater adverse impact on the receiving river than agricultural runoff.

The impact of treated sewage wastewater discharges on the phosphorus levels and hydrology of two second order rivers flowing into the Thames.

Rivers Bourne and Hogsmill, urban tributaries of the Thames, were sampled up and downstream of sewage treatment works (STWs) wastewaters outflows. River water was analysed for total phosphorus (TP) and soluble reactive phosphorus (SRP) and, in conjunction with river flow data, this study aimed to assess the impact of treated wastewaters on P concentrations in rivers where wastewater volumes frequently exceed those of the underlying river and to consider whether these rivers are likely to achieve "good ecological status" under the Water Framework Directive (WFD). P concentrations downstream of the STW discharge points were generally an order of magnitude greater than upstream, the flow weighted mean concentration in the River Bourne increased from 0.078 mg SRP l(-1) to 0.45 mg SRP l(-1) downstream of the input source. In the Hogsmill, the flow weighted mean concentration rose from 0.19 mg SRP l(-1) to 1.78 mg SRP l(-1) downstream of the input source prior to the introduction of P removal at the STW. Once P removal commenced, flow weighted mean concentrations downstream of the STW reduced to 0.56 mg SRP l(-1). Headwaters in the River Bourne, upstream of the STW outflow showed evidence of irregular, minor, diffuse inputs but overall mean figures indicate that the proposed UK Technical Advisory Group (UK TAG) for the WFD limit of 0.12 mg SRP l(-1) would be met. Headwaters in the Hogsmill are subject to small, continuous discharges of sewage effluent, sufficient to raise SRP levels above the UK TAG limit. Downstream, neither river meets the UKTAG recommendations in terms of P, despite the use of P-stripping processes at both STWs, an indication that current discharge consents for P concentrations in wastewaters are too high.