Quantifying the total and bioavailable polycyclic aromatic hydrocarbons and dioxins in biochars.

Biochar soil amendment is advocated to mitigate climate change and improve soil fertility. A concern though, is that during biochar preparation PAHs and dioxins are likely formed. These contaminants can possibly be present in the biochar matrix and even bioavailable to exposed organisms. Here we quantify total and bioavailable PAHs and dioxins in a suite of over 50 biochars produced via slow pyrolysis between 250 and 900 °C, using various methods and biomass from tropical, boreal, and temperate areas. These slow pyrolysis biochars, which can be produced locally on farms with minimum resources, are also compared to biochar produced using the industrial methods of fast pyrolysis and gasification. Total concentrations were measured with a Soxhlet extraction and bioavailable concentrations were measured with polyoxymethylene passive samplers. Total PAH concentrations ranged from 0.07 µg g(-1) to 3.27 µg g(-1) for the slow pyrolysis biochars and were dependent on biomass source, pyrolysis temperature, and time. With increasing pyrolysis time and temperature, PAH concentrations generally decreased. These total concentrations were below existing environmental quality standards for concentrations of PAHs in soils. Total PAH concentrations in the fast pyrolysis and gasification biochar were 0.3 µg g(-1) and 45 µg g(-1), respectively, with maximum levels exceeding some quality standards. Concentrations of bioavailable PAHs in slow pyrolysis biochars ranged from 0.17 ng L(-1) to 10.0 ng L(-1)which is lower than concentrations reported for relatively clean urban sediments. The gasification produced biochar sample had the highest bioavailable concentration (162 ± 71 ng L(-1)). Total dioxin concentrations were low (up to 92 pg g(-1)) and bioavailable concentrations were below the analytical limit of detection. No clear pattern of how strongly PAHs were bound to different biochars was found based on the biochars' physicochemical properties.

Anaerobic treatment of olive mill wastewater and piggery effluents fermented with Candida tropicalis.

Olive mill wastewater (OMW) contains high concentrations of phenolic compounds that are inhibitory to many microorganisms making it difficult to treat biologically prior to discharge in waterways. The total mono-cyclic phenol reduction in OMW in this study was carried out by aerobic pre-treatment using the yeast Candida tropicalis in a 18 L batch reactor at 30 degrees C for 12 days followed by anaerobic co-digestion. A COD removal of 62% and a reduction in the total mono-cyclic phenol content by 51% of the mixture was achieved in the aerobic pre-treatment. Pig slurry was added as co-substrate to supplement the low nitrogen levels in the olive mill wastewater. Subsequent anaerobic treatment was carried out in a 20L fixed-bed reactor at 37 degrees C and HRT between 11 and 45 days. After a long start-up period, the OLR was increased from 1.25 to 5 kg COD m(-3)day(-1) during the last 30 days, resulting in subsequent increase in overall COD removal and biogas production, up to maximum values of 85% and 29 L(biogas)L(reactor)(-1)day(-1), respectively. Methane content of the biogas produced from the anaerobic digestion ranged between 65% and 74%.

Characterization of the cell surface and cell wall chemistry of drinking water bacteria by combining XPS, FTIR spectroscopy, modeling, and potentiometric titrations.

Aquabacterium commune, a predominant member of European drinking water biofilms, was chosen as a model bacterium to study the role of functional groups on the cell surface that control the changes in the chemical cell surface properties in aqueous electrolyte solutions at different pH values. Cell surface properties of A. commune were examined by potentiometric titrations, modeling, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy. By combining FTIR data at different pH values and potentiometric titration data with thermodynamic model optimization, the presence, concentration, and changes of organic functional groups on the cell surface (e.g., carboxyl, phosphoryl, and amine groups) were inferred. The pH of zero proton charge, pH(zpc) = 3.7, found from titrations of A. commune at different electrolyte concentrations and resulting from equilibrium speciation calculations suggests that the net surface charge is negative at drinking water pH in the absence of other charge determining ions. In situ FTIR was used to describe and monitor chemical interactions between bacteria and liquid solutions at different pH in real time. XPS analysis was performed to quantify the elemental surface composition, to assess the local chemical environment of carbon and oxygen at the cell wall, and to calculate the overall concentrations of polysaccharides, peptides, and hydrocarbon compounds of the cell surface. Thermodynamic parameters for proton adsorption are compared with parameters for other gram-negative bacteria. This work shows how the combination of potentiometric titrations, modeling, XPS, and FTIR spectroscopy allows a more comprehensive characterization of bacterial cell surfaces and cell wall reactivity as the initial step to understand the fundamental mechanisms involved in bacterial adhesion to solid surfaces and transport in aqueous systems.

Investigating and modelling the development of septic sewage in filled sewers under static conditions: a lab-scale feasibility study.

This paper describes a lab-scale study of the physical and bio-chemical processes associated with the development of septic conditions in sewer pipes filled with static sewage. The study has concentrated on the uptake of oxygen (OUR) and the subsequent changes in chemical oxygen demand (COD), sulphate, sulphide and nitrate concentration and the formation of volatile fatty acids (VFA). OUR of raw sewage ranged from 2 to 13 mg L(-1) h(-1). Apparent nitrate uptake and sulphide generation rates in static sewage varied between 0.2-0.7 mgNO(3) L(-1) h(-1) and 0.02-0.05 mgH(2)S-S L(-1) h(-1), respectively. A logistic function was used to simulate the sulphide generation process in static sewage. It was found that total COD (COD(total)) influenced the apparent sulphide generation rate while nitrate concentrations greater than 4 mg L(-1) controlled the onset of sulphide production in experiments without added sediment phase. Introducing a sediment phase appeared to accelerate hydrolysis and fermentation processes as evidenced by 5-14 times greater dissolved COD generation rates in the bulk water phase.