Determination of organic fluorinated compounds content in complex samples through combustion ion chromatography methods: a way to define a "Total Per- and Polyfluoroalkyl Substances (PFAS)" parameter?

Emerging contaminants are a growing concern for scientists and public authorities. The group of per-polyfluoroalkyl substances (PFAS), known as 'forever chemicals', in complex environmental liquid and solid matrices was analysed in this study. The development of global analytical methods based on combustion ion chromatography (CIC) is expected to provide accurate picture of the overall PFAS contamination level via the determination of extractable organic fluorine (EOF) and adsorbable organic fluorine (AOF). The obtained results may be put into perspective with other methods such as targeted analyses (LC-MS/MS). The impact of pH, the presence of dissolved organic carbon and suspended particles on AOF measurements were explored. The effectiveness of the washing step to remove adsorbed inorganic fluorine (IF) has been proven for samples containing up to 8 mgF.L-1. CIC-based methods showed good repeatability and reproducibility for the complex matrices studied. Environmental applications of these methods have been tested. AOF and EOF analyses could explain between 1 % and 23 % and 0.1 % to 2 % of total organic fluorine (TOF), respectively. The sum of PFAS compounds expressed as fluorine could explain from 0.2 % to 11 % and from 0.003 % to 5 % for AOF and EOF, respectively. These results also suggest that some fluorinated compounds are not adsorbed or extractable and/or lost by volatilisation during the application of AOF and EOF analytical procedure. These findings highlight that AOF and EOF are not entirely efficient as proxy to assess "total PFAS" for assessing environmental contamination by PFAS. However, these methods could still be applied to gain a better understanding of the sources and fate of PFAS in the environment.

Build-up and impact of volatile fatty acids on E. coli and A. lumbricoides during co-digestion of urine diverting dehydrating toilet (UDDT-F) faeces.

This study examined the potential of Escherichia coli (E. coli) and Ascaris lumbricoides (A. lumbricoides) eggs inactivation in faecal matter coming from urine diverting dehydrating toilets (UDDT-F) by applying high concentrations of volatile fatty acids (VFAs) during anaerobic stabilization. The impact of individual VFAs on E. coli and A. lumbricoides eggs inactivation in UDDT-F was assessed by applying various concentrations of store-bought acetate, propionate and butyrate. High VFA concentrations were also obtained by performing co-digestion of UDDT-F with organic market waste (OMW) using various mixing ratios. All experiments were performed under anaerobic conditions in laboratory scale batch assays at 35±1 °C. A correlation was observed between E. coli log inactivation and VFA concentration. Store bought VFA spiked UDDT-F substrates achieved E. coli inactivation up to 4.7 log units/day compared to UDDT-F control sample that achieved 0.6 log units/day. In co-digesting UDDT-F and organic market waste (OMW), a ND-VFA concentration of 4800-6000 mg/L was needed to achieve E. coli log inactivation to below detectable levels and complete A. lumbricoides egg inactivation in less than four days. E. coli and A. lumbricoides egg inactivation was found to be related to the concentration of non-dissociated VFA (ND-VFA), increasing with an increase in the OMW fraction in the feed substrate. Highest ND-VFA concentration of 6500 mg/L was obtained at a UDDT-F:OMW ratio 1:1, below which there was a decline, attributed to product inhibition of acidogenic bacteria. Results of our present research showed the potential for E. coli and A. lumbricoides inactivation from UDDT-F up to WHO standards by allowing VFA build-up during anaerobic stabilization of faecal matter.

Lactic acid fermentation of human excreta for agricultural application.

Studies show that source separated human excreta have a fertilizing potential with benefits to plant growth and crop yield similar or exceeding that of mineral fertilizers. The main challenges in fertilizing with excreta are pathogens, and an increased risk of eutrophication of water bodies in case of runoff. This review shows that lactic acid fermentation of excreta reduces the amount of pathogens, minimizes the nutrient loss and inhibits the production of malodorous compounds, thus increasing its agricultural value. Pathogens (e.g., Enterobacteriacea, Staphylococcus and Clostridium) can be reduced by 7 log CFUg-1 during 7-10 days of fermentation. However, more resistant pathogens (e.g. Ascaris) are not always efficiently removed. Direct application of lacto-fermented faeces to agriculture may be constrained by incomplete decomposition, high concentrations of organic acids or insufficient hygienization. Post-treatment by adding biochar, vermi-composting, or thermophilic composting stabilizes and sanitizes the material. Pot and field experiments on soil conditioners obtained via lactic acid fermentation and post treatment steps (composting or biochar addition) demonstrated increased crop yield and growth, as well as improved soil quality, in comparison to unfertilized controls.

Struvite precipitation from urine - Influencing factors on particle size.

Struvite crystallisation is a fast and reliable phosphorus removal and recovery process for concentrated waste streams - such as hydrolysed human urine. In order to optimise P-elimination efficiency, it is beneficial to obtain larger particle sizes: they are easier to separate and less prone to wash-out than smaller particles. This paper presents the results of a study on the effect of process parameters on particle size in a single step struvite precipitation. Crystals formed in batch experiments with real hydrolysed urine were shown to have an average size of >90 microm at pH 9 and 20 degrees C. This is reduced to 45 microm when changing stirrer type. Particle size increases with lower supersaturation. The results showed that under otherwise constant conditions, particle size decreases with lower temperature and has a minimum between pH 9 and 10. Deviating trends are observed at pH <8. Struvite formation in a CSTR (continuously stirred tank reactor) process was shown to be a reliable stable process that does not require any pH control. A method based on conductivity measurement is presented to estimate ionic strength, which is needed for equilibrium calculations.

The behaviour of pharmaceuticals and heavy metals during struvite precipitation in urine.

Separating urine from wastewater at the source reduces the costs of extensive wastewater treatment. Recovering the nutrients from urine and reusing them for agricultural purposes adds resource saving to the benefits. Phosphate can be recovered in the form of struvite (magnesium ammonium phosphate). In this paper, the behaviour of pharmaceuticals and heavy metals during the precipitation of struvite in urine is studied. When precipitating struvite in urine spiked with hormones and non-ionic, acidic and basic pharmaceuticals, the hormones and pharmaceuticals remain in solution for more than 98%. For heavy metals, initial experiments were performed to study metal solubility in urine. Solubility is shown to be affected by the chemical conditions of stored and therefore hydrolysed urine. Thermodynamic modelling reveals low or very low equilibrium solute concentrations for cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb). Experiments confirmed Cd, Cu and Pb carbonate and hydroxide precipitation upon metal addition in stored urine with a reaction half-life of ca. 7 days. For all metals considered, the maximum specific metal concentrations per gram phosphate or nitrogen showed to be typically several orders of magnitudes lower in urine than in commercially available fertilizers and manure. Heavy metals in struvite precipitated from normal stored urine could not be detected. Phosphate recovery from urine over struvite precipitation is shown to render a product free from most organic micropollutants and containing only a fraction of the already low amounts of heavy metals in urine.

Struvite precipitation thermodynamics in source-separated urine.

Struvite (MgNH(4)PO(4).6H(2)O) precipitation eliminates phosphate efficiently from urine, a small but highly concentrated stream in the total flux of domestic wastewater. Precipitation experiments with hydrolysed urine evaluated the solubility product of struvite. The stored and fully hydrolysed urine had an ionic strength of between 0.33 and 0.56M and required the estimation of activity coefficients. From our data, we identified the Davies approximation with the two constants A=0.509 and B=0.3 as agreeing best with our laboratory results. The standard solubility product K(s)(0)=f(1)[NH4(+)]f(2)[Mg2+]f(3)[PO(4)(3-)] ([ ]=concentration of the species; f(x)=corresponding activity coefficient) of struvite in urine was found to be 10(-13.26+/-0.057) at 25 degrees C and the enthalpy of struvite formation DeltaH was 22.6(+/-1.1) kJmol(-1). The equilibrium calculations required the following dissolved complexes: [MgCO(3)](aq), [MgHCO(3)](+), [MgPO(4)](-), [NH4HPO4and [NaHPO(4)](-) and to a lesser extent [MgSO(4)](aq) and [NH(4)SO(4)](-). Organic complexes do not seem to influence the solubility product substantially. For practical purposes, a conditional solubility product K(s)(cond)=[Mg(aq)].[NH(4)(+)+NH(3)].[P(ortho)]=10(-7.57)M(3) was derived to calculate struvite solubility in urine at 25 degrees C, pH=9.0 and ionic strength I=0.4M directly from measured concentrations.

Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor.

A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H2/CO2, no apparent inhibition occurred up to a concentration of 500 mg l(-1). When strain WW1 was co-cultured under the same conditions with the methanol-utilizing, non-sulfate-reducing bacteria, Thermotoga lettingae and Moorella mulderi, both originating from the same bioreactor, growth and sulfide formation were observed up to 430 mg l(-1). These results indicated that in the co-cultures, a major part of the electron flow was directed from methanol via H2/CO2 to the reduction of sulfate to sulfide. Besides methanol, acetate, and hydrogen, strain WW1 was also able to use formate, malate, fumarate, propionate, succinate, butyrate, ethanol, propanol, butanol, isobutanol, with concomitant reduction of sulfate to sulfide. In the absence of sulfate, strain WW1 grew only on pyruvate and lactate. On the basis of 16S rRNA analysis, strain WW1 was most closely related to Desulfotomaculum thermocisternum and Desulfotomaculum australicum. However, physiological properties of strain WW1 differed in some aspects from those of the two related bacteria.