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BackgroundManufactured silver nanoparticles (AgNPs) are one of the most commonly used nanomaterials in consumer goods and consequently their concentrations in wastewater and hence wastewater treatment plants are predicted to increase. We investigated the fate of AgNPs in sludge that was subjected to aerobic and anaerobic treatment and the impact of AgNPs on microbial processes and communities. The initial identification of AgNPs in sludge was carried out using transmission electron microscopy (TEM) with energy dispersive X-ray (EDX) analysis. The solid phase speciation of silver in sludge and wastewater influent was then examined using X-ray absorption spectroscopy (XAS). The effects of transformed AgNPs (mainly Ag-S phases) on nitrification, wastewater microbial populations and, for the first time, methanogenesis was investigated.ResultsSequencing batch reactor experiments and anaerobic batch tests, both demonstrated that nitrification rate and methane production were not affected by the addition of AgNPs [at 2.5 mg Ag L-1 (4.9 g L-1 total suspended solids, TSS) and 183.6 mg Ag kg -1 (2.9 g kg-1 total solids, TS), respectively].The low toxicity is most likely due to AgNP sulfidation. XAS analysis showed that sulfur bonded Ag was the dominant Ag species in both aerobic (activated sludge) and anaerobic sludge. In AgNP and AgNO3 spiked aerobic sludge, metallic Ag was detected (~15%). However, after anaerobic digestion, Ag(0) was not detected by XAS analysis. Dominant wastewater microbial populations were not affected by AgNPs as determined by DNA extraction and pyrotag sequencing. However, there was a shift in niche populations in both aerobic and anaerobic sludge, with a shift in AgNP treated sludge compared with controls. This is the first time that the impact of transformed AgNPs (mainly Ag-S phases) on anaerobic digestion has been reported.ConclusionsSilver NPs were transformed to Ag-S phases during activated sludge treatment (prior to anaerobic digestion). Transformed AgNPs, at predicted future Ag wastewater concentrations, did not affect nitrification or methanogenesis. Consequently, AgNPs are very unlikely to affect the efficient functioning of wastewater treatment plants. However, AgNPs may negatively affect sub-dominant wastewater microbial communities.

The biodegradability and bioavailability of hydrolysis-limited substrates under anaerobic (and aerobic) conditions can be represented by two key parameters--degradability (f(d)), or the percentage that can be effectively be destroyed during digestion, and first order hydrolysis coefficient (k(hyd)), or the speed at which material breaks down. Biochemical methane potential (BMP) testing uses a batch test (in triplicate), and by fitting against a first order model, can fit both parameters in the same test. BMP testing is now being widely used for anaerobic process feasibility and design purposes, and standardisation efforts are ongoing. In this paper, we address a number of key issues relating to the test method and its analysis. This includes proposal of a new fitting and parameter estimation method, evaluation of the impact of inoculum to substrate ratio on fitted parameters, and comparison to performance in continuous systems. The new parameter estimation technique provides an estimate of parameter uncertainty and correlation, and is clearly more suitable than model transformation and linear regression. An inoculum volume ratio of at least 50% (2:1 on VS basis) was required on a cellulose substrate to use methane production as primary indicator, as found by comparing methane production and solubilisation of cellulose. Finally, on a typical material, waste activated sludge, the batch test was slightly conservative in terms of degradability and rate, indicating a bias in the BMP test. The test is a cost-effective and capable method to evaluate potential substrates, but it should be noted that it is generally conservative, especially if sub-optimal inoculum is used.

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