Household mixed plastic waste derived adsorbents for CO2 capture: A feasibility study.

The feasibility of producing activated carbon (AC) from real Household Mixed Plastic Waste (HMPW) comprising of LDPE, HDPE, PP, PS, and PET for carbon capture via direct carbonisation followed by microwave-assisted or conventional thermally assisted chemical activation was investigated. A microwave-assisted activation procedure was adopted to assess the impact on the CO2 capture capacity of the resulting AC using both a lower temperature (400 °C vs. 700 °C) and a shorter duration (5 vs. 120 mins) than that required for conventional activation. The results obtained showed that the AC yield was 71 and 78% for the conventional and microwave-assisted samples, respectively. Microwave activation consumed five-fold less energy (0.19 kWh) than the conventional activation (0.98 kWh). Thermal stability results indicated total weight loss of 10.0 and 8.3 wt%, respectively, for conventional and microwave-activated samples over the temperature range of 25-1000 °C, with ACs from both activation routes displaying a type 1 nitrogen isotherm. The dynamic CO2 uptake capacity at 1 bar and 25 °C was 1.53 mmol/g, with maximum equilibrium uptake ranging between 1.32 and 2.39 mmol/g at temperatures (0-50 °C) and 1 bar for the conventionally activated AC. The analogous microwave-activated sample showed a higher dynamic CO2 uptake of 1.62 mmol/g and equilibrium uptake in the range 1.58-2.88 mmol/g under equivalent conditions. The results therefore indicate that microwave activation results in enhanced carbon capture potential. To the best of our knowledge, this is the first-time microwave heating has been employed to convert household mixed plastic wastes directly into ACs for carbon capture applications. This report therefore demonstrates that the management of mixed plastics could lead to the development of a circular economy through the conversion of waste into value-added materials.

Research ReportDiurnal global ocean surface pCO2 and air-sea CO2 flux reconstructed from spaceborne LiDAR data.

The ocean absorbs a significant amount of carbon dioxide (CO2) from the atmosphere, helping regulate Earth's climate. However, our knowledge of ocean CO2 sink levels remains limited. This research focused on assessing daily changes in ocean CO2 sink levels and air-sea CO2 exchange, using a new technique. We used LiDAR technology, which provides continuous measurements during day and night, to estimate global ocean CO2 absorption over 23 years. Our model successfully reproduced sea surface partial pressure of CO2 data. The results suggest the total amount of CO2 absorbed by oceans is higher at night than during the day. This difference arises from a combination of factors like temperatures, winds, photosynthesis, and respiration. Understanding these daily fluctuations can improve predictions of ocean CO2 uptake. It may also help explain why current carbon budget calculations are not fully balanced-an issue scientists have grappled with. Overall, this pioneering study highlights the value of LiDAR's unique day-night ocean data coverage. The findings advance knowledge of ocean carbon cycles and their role in climate regulation. They underscore the need to incorporate day-night variability when assessing the ocean's carbon sink capacity.

Atmospheric Thermodynamic Profiling through the Use of a Micro-Pulse Raman Lidar System: Introducing the Compact Raman Lidar MARCO.

It was for a long time believed that lidar systems based on the use of high-repetition micro-pulse lasers could be effectively used to only stimulate atmospheric elastic backscatter echoes, and thus were only exploited in elastic backscatter lidar systems. Their application to stimulate rotational and roto-vibrational Raman echoes, and consequently, their exploitation in atmospheric thermodynamic profiling, was considered not feasible based on the technical specifications possessed by these laser sources until a few years ago. However, recent technological advances in the design and development of micro-pulse lasers, presently achieving high UV average powers (1-5 W) and small divergences (0.3-0.5 mrad), in combination with the use of large aperture telescopes (0.3-0.4 m diameter primary mirrors), allow one to presently develop micro-pulse laser-based Raman lidars capable of measuring the vertical profiles of atmospheric thermodynamic parameters, namely water vapor and temperature, both in the daytime and night-time. This paper is aimed at demonstrating the feasibility of these measurements and at illustrating and discussing the high achievable performance level, with a specific focus on water vapor profile measurements. The technical solutions identified in the design of the lidar system and their technological implementation within the experimental setup of the lidar prototype are also carefully illustrated and discussed.

Investigating the challenges of biogas provision in water limited environments through laboratory scale biodigesters.

The potential for biogas provision through household-scale anaerobic digestion in rural sub-Saharan Africa is limited due to perceived water shortages. The most common substrate is animal dung diluted 1:1 with water. Two experimental methods tested the potential of reducing water demand. The first experiment compared the chemical oxygen demand (COD) and volatile solid removal of four cow dung dilutions ranging from 3.5-10.6% total solids. In the second experiment, bioslurry filtrate was recirculated back into the fresh substrate at different concentrations. The highest COD removal rate of 28.3% was obtained from mixing equal volumes of dung with filtrate (mean total solids 7.4%) while the highest methane production rate of 0.40 g/L/day, calculated from COD balance, was obtained from undiluted cow dung (total solids 10.6%). Results suggest the potential for a 75-100% reduction in water demand.

Comprehensive, Continuous, and Vertical Measurements of Seawater Constituents with Triple-Field-of-View High-Spectral-Resolution Lidar.

Measuring the characteristics of seawater constituent is in great demand for studies of marine ecosystems and biogeochemistry. However, existing techniques based on remote sensing or in situ samplings present various tradeoffs with regard to the diversity, synchronism, temporal-spatial resolution, and depth-resolved capacity of their data products. Here, we demonstrate a novel oceanic triple-field-of-view (FOV) high-spectral-resolution lidar (HSRL) with an iterative retrieval approach. This technique provides, for the first time, comprehensive, continuous, and vertical measurements of seawater absorption coefficient, scattering coefficient, and slope of particle size distribution, which are validated by simulations and field experiments. Furthermore, it depicts valuable application potentials in the accuracy improvement of seawater classification and the continuous estimation of depth-resolved particulate organic carbon export. The triple-FOV HSRL with high performance could greatly increase the knowledge of seawater constituents and promote the understanding of marine ecosystems and biogeochemistry.

Shipborne oceanic high-spectral-resolution lidar for accurate estimation of seawater depth-resolved optical properties.

Lidar techniques present a distinctive ability to resolve vertical structure of optical properties within the upper water column at both day- and night-time. However, accuracy challenges remain for existing lidar instruments due to the ill-posed nature of elastic backscatter lidar retrievals and multiple scattering. Here we demonstrate the high performance of, to the best of our knowledge, the first shipborne oceanic high-spectral-resolution lidar (HSRL) and illustrate a multiple scattering correction algorithm to rigorously address the above challenges in estimating the depth-resolved diffuse attenuation coefficient Kd and the particulate backscattering coefficient bbp at 532 nm. HSRL data were collected during day- and night-time within the coastal areas of East China Sea and South China Sea, which are connected by the Taiwan Strait. Results include vertical profiles from open ocean waters to moderate turbid waters and first lidar continuous observation of diel vertical distribution of thin layers at a fixed station. The root-mean-square relative differences between the HSRL and coincident in situ measurements are 5.6% and 9.1% for Kd and bbp, respectively, corresponding to an improvement of 2.7-13.5 and 4.9-44.1 times, respectively, with respect to elastic backscatter lidar methods. Shipborne oceanic HSRLs with high performance are expected to be of paramount importance for the construction of 3D map of ocean ecosystem.

Experimental investigation of a new process for treatment and valorisation of pot ale wastewaters.

This study investigated an innovative process for the treatment and valorisation of pot ale wastewater. The first phase was to balance the pH to precipitate nitrogen, phosphorus and magnesium, recovering them as fertiliser; the second phase investigated the evaporation of water, reducing the volume of liquid to be transported to an anaerobic digester. In the pH balancing phase we investigated the effect of the final pH, in the range 8-11, on the removal of calcium, magnesium, ammonia, phosphorus and copper. We observed that, for all the species, most of the precipitation occurred when pH was increased from 8 to 9. By pH balancing, a removal from the liquid phase of up to 65% of ammonia and 60% of total phosphorus was obtained. Calcium and magnesium also precipitated from the liquid phase, giving solids with the following composition, calculated from liquid phase measurements: 24-27% magnesium, 4-5% nitrogen, 16-18% phosphorus. We investigated the evaporation process at pH 6 and 10 and at atmospheric pressure and under vacuum. The results showed that only a few % of the chemical oxygen demand (COD) evaporates, indicating very little loss of organic substance for anaerobic digestion. Mass balances for this process in a medium-size whisky distillery were also carried out.

Quantification of hydrocarbon species on surfaces by combined microbalance-FTIR.

Absorption coefficients for the asymmetric stretching modes of CH3 and CH2 groups formed by adsorbing alkyl chained species from the vapour phase onto two different adsorbents; a γ-alumina support material and a supported metal catalyst have been determined using a custom made thermogravimetric-infrared cell. Results show that despite variations in the individually calculated absorption coefficients (ca. ±20%), the ratio of the absorption coefficients (CH2:CH3) remained consistent despite employing adsorbates of varying chain length and functionality, and despite the choice of adsorbents which exhibited different surface areas and light scattering characteristics. The use of this absorption coefficient ratio has been shown to be applicable in the quantification of the average chain length of multiple adsorbed species of differing chain length. The potential for applying this to scenarios where reactions on surfaces are monitored is discussed.

LIDAR developments at Clermont-Ferrand--France for atmospheric observation.

We present a Rayleigh-Mie-Raman LIDAR system in operation at Clermont-Ferrand (France) since 2008. The system provides continuous vertical tropospheric profiles of aerosols, cirrus optical properties and water vapour mixing ratio. Located in proximity to the high altitude Puy de Dôme station, labelled as the GAW global station PUY since August 2014, it is a useful tool to describe the boundary layer dynamics and hence interpret in situ measurements. This LIDAR has been upgraded with specific hardware/software developments and laboratory calibrations in order to improve the quality of the profiles, calibrate the depolarization ratio, and increase the automation of operation. As a result, we provide a climatological water vapour profile analysis for the 2009-2013 period, showing an annual cycle with a winter minimum and a summer maximum, consistent with in-situ observations at the PUY station. An overview of a preliminary climatology of cirrus clouds frequency shows that in 2014, more than 30% of days present cirrus events. Finally, the backscatter coefficient profile observed on 27 September 2014 shows the capacity of the system to detect cirrus clouds at 13 km altitude, in presence of aerosols below the 5 km altitude.

Operation of fill-and-draw reactors fed with bisphenol A as sole carbon and energy source.

While there is ample evidence in the literature that many organic xenobiotics can be biodegraded as sole carbon and energy source by pure batch cultures of selected microorganisms, the same evidence is very limited for continuous or semi-continuous mixed-culture processes simulating biological wastewater treatment plants. This study investigates for the first time whether Bisphenol A (BPA) can be removed and used as sole carbon and energy source by mixed microbial cultures in a semi-continuous process. Four fill and draw bioreactors were inoculated with unacclimated soil and operated at various hydraulic retention times (HRT), in the range of 1.7-4.2 d, using a feed composed solely of BPA (115 mg/l), and mineral salts. At steady-state, the BPA removal in the four reactors varied in the range 7.5-19% and did not show a significant trend with the HRT. The maximum growth rate on BPA was measured in the range 0.29-1.54 d-1.

Metabolic analysis of the removal of formic acid by unacclimated activated sludge.

This paper investigates the removal of formic acid by unacclimated biomass from a municipal activated sludge wastewater treatment plant. The biomass was initially able to remove formic acid, but its removal rate and Oxygen Uptake Rate (OUR) decreased with time, until formic acid removal stopped before the formic acid had been exhausted. Formaldehyde was removed in a similar way, whereas the same biomass was simultaneously able to grow and store PHAs when acetic acid was used as substrate. Batch tests with glycine and (13)C NMR analysis were performed, showing that unacclimated biomass was not able to synthesize all the metabolic intermediates from formic acid alone. At least glycine needed to be externally supplemented, in order to activate the serine synthesis pathway. A small amount of formic acid removal in the absence of growth was also possible through formaldehyde formation and its further conversion to formalin (1,2-formaldehyde dimer), whereas no PHAs were formed.

High-rate anaerobic treatment of Fischer-Tropsch wastewater in a packed-bed biofilm reactor.

This study investigates the anaerobic treatment of an industrial wastewater from a Fischer-Tropsch (FT) process in a continuous-flow packed-bed biofilm reactor operated under mesophilic conditions (35 degrees C). The considered synthetic wastewater has an overall chemical oxygen demand (COD) concentration of around 28g/L, mainly due to alcohols. A gradual increase of the organic load rate (OLR), from 3.4gCOD/L/d up to 20gCOD/L/d, was adopted in order to overcome potential inhibitory effects due to long-chain alcohols (>C6). At the highest applied OLR (i.e., 20gCOD/L/d) and a hydraulic retention time of 1.4d, the COD removal was 96% with nearly complete conversion of the removed COD into methane. By considering a potential of 200tCOD/d to be treated, this would correspond to a net production of electric energy of about 8x10(7)kWh/year. During stable reactor operation, a COD balance and batch tests showed that about 80% of the converted COD was directly metabolized through H(2)(-) and acetate-releasing reactions, which proceeded in close syntrophic cooperation with hydrogenotrophic and acetoclastic methanogenesis (contributing to about 33% and 54% of overall methane production, respectively). Finally, energetic considerations indicated that propionic acid oxidation was the metabolic conversion step most dependent on the syntrophic partnership of hydrogenotrophic methanogens and accordingly the most susceptible to variations of the applied OLR or toxicity effects.

Effect of the length of the cycle on biodegradable polymer production and microbial community selection in a sequencing batch reactor.

The effect of the length of the cycle on the enrichment and selection of mixed cultures in sequencing batch reactors (SBRs) has been studied, with the aim of biodegradable polymers (namely, polyhydroxyalkanoates (PHAs)) production from organic wastes. At a fixed feed concentration (20 gCOD/L) and organic loading rate (20 gCOD/L/day), the SBR was operated at different lengths of the cycle, in the range 1-8 h. Process performance was measured by considering the rates and yields of polymer storage and of the competing phenomenon of growth. The selected biomass was enriched with microorganisms that were able to store PHAs at high rates and yields only when the length of the cycle was 2 or 4 h, even though in these conditions the process was unstable. On the other hand, when the length of the cycle was 1 or 8 h, the dynamic response of the selected microorganisms was dominated by growth. The best process performance was characterized by storage rates in the range 500-600 mgCOD/gCOD/h and storage yields of 0.45-0.55 COD/COD. The corresponding productivity of the process was in the range 0.25-0.30 gPHA/L/h, the highest values obtained until now for mixed cultures. The microbial composition of the selected biomasses was analyzed through denaturing gradient gel electrophoresis (DGGE) and reverse-transcriptase denaturing gradient gel electrophoresis (RT-DGGE). The instability of the runs characterized by high storage rate was associated with a higher microbial heterogeneity compared to the runs with a stable growth response.

Effect of periodic feeding on substrate uptake and storage rates by a pure culture of Thiothrix (CT3 strain).

A pure culture of Thiothrix strain CT3 has been aerobically cultured under periodic acetate feeding in a Sequencing Batch Reactor (SBR) at volumetric organic load rate of 0.12gCODL(-1)d(-1). Two different culture residence times (12d or 20d) were adopted as well as two different feed frequencies (1 and 4d(-1), for each culture residence time), the volumetric organic load rate being the same under all conditions. The transient response of the microorganism to the periodic acetate feed was investigated through batch tests with biomass withdrawn from the SBR, as function of the different SBR operating conditions. In all tested conditions, a quick transient response to the acetate spike was observed with fast increase of acetate uptake rate (ranging from 71 to 247mgCODgCOD(-1)h(-1)). This transient response was mainly due to acetate storage in form of poly-hydroxybutyrate (ranging from 45% to 64% of the observed yield) whereas the growth response (i.e. increase of production rate of active biomass) generally played a minor role (ranging from 21% to 38% of the observed yield). Apart from this general trend, culture residence time as well as feed frequency had a strong impact on transient behaviour of cultured cells. The overall transient response (i.e. maximum specific substrate removal rate) increased as culture residence time decreased or as feed frequency increased. Moreover, the ratio of storage response and growth response increased as the overall transient response decreased, i.e. the storage response was preferentially maintained when cells presented a lower transient response. The ability of the cells to increase their growth rate with respect to SBR average value was the lowest under the most unfavourable conditions (residence time 20d, feed frequency 1d(-1)) and increased with the increase in maximum substrate uptake rate.

Effect of the applied organic load rate on biodegradable polymer production by mixed microbial cultures in a sequencing batch reactor.

This article studies the operation of a new process for the production of biopolymers (polyhydroxyalkanoates, PHAs) at different applied organic load rates (OLRs). The process is based on the aerobic enrichment of activated sludge to obtain mixed cultures able to store PHAs at high rates and yields. A mixture of acetic, lactic, and propionic acids at different concentrations (in the range 8.5-31.25 gCOD/L) was fed every 2 h in a sequencing batch reactor (SBR). The resulting applied OLR was in the range 8.5-31.25 gCOD/L/day. Even though, as expected, the increase in the OLR caused an increase in biomass concentration (up to about 8.7 g COD/L), it also caused a relevant decrease of maximal polymer production rate. This decrease in polymer production rate was related to the different extent of "feast and famine" conditions, as function of the applied OLR and of the start-up conditions. As a consequence the best performance of the process was obtained at an intermediate OLR (20 gCOD/L/day) where both biomass productivity and PHA storage were high enough. However, at this high OLR the process was unstable and sudden decrease of performance was also observed. The sludge characterized by the highest PHA storage response was investigated by 16S rDNA clone library. The clone library contained sequences mostly from PHA producers (e.g., Alcaligenes and Comamonas genera); however many genera and among them, one of the dominant (Thauera), were never described before in relation to PHA storage response.

Glutamic acid removal and PHB storage in the activated sludge process under dynamic conditions.

Glutamic acid removal in the activated sludge process is studied herein, primarily the formation of storage polymers under dynamic conditions. The activated sludge process was operated by using a sequencing batch reactor (sludge age of 6 d) fed with a synthetic mixture of readily available carbon sources, including glutamic acid. Removal of glutamic acid as the only carbon sources was studied in batch tests, along with oxygen consumption, ammonia uptake-release, and formation of storage polymers. It was found that poly-3-hydroxybutyrate (PHB) was stored and that the storage also occurred simultaneously to biomass growth. PHB storage accounted for 16% of the overall solids that were formed from glutamic acid, as the average value of nine batch tests. Neither other Polyhydroxyalkanoates nor polyglutamic acid were detected. Nuclear magnetic resonance analysis, performed on biomass extracts, allowed us to clarify the main metabolic pathways involved in glutamic acid removal and, in particular, the pathways involved in PHB storage. It was found that glutamic acid enters the Krebs cycle as alpha-ketoglutaric acid and exits to form pyruvic acid and then acetyl-CoA, which is the starting point of PHB production pathway.

Biodegradable polymers from organic acids by using activated sludge enriched by aerobic periodic feeding.

This article describes a new process for the production of biopolymers (polyhydroxyalkanoates, PHAs) based on the aerobic enrichment of activated sludge to obtain mixed cultures able to store PHAs at high rates and yields. Enrichment was obtained through the selective pressure established by feeding the carbon source in a periodic mode (feast and famine regime) in a sequencing batch reactor. A concentrated mixture of acetic, lactic, and propionic acids (overall concentration of 8.5 gCOD L(-1)) was fed every 2 h at 1 day(-1) overall dilution rate. Even at such high organic load (8.5 gCOD L(-1) day(-1)), the selective pressure due to periodic feeding was effective in obtaining a biomass with a storage ability much higher than activated sludges. The immediate biomass response to substrate excess (as determined thorough short-term batch tests) was characterized by a storage rate and yield of 649 mgPHA (as COD) g biomass (as COD)(-1) h(-1) and 0.45 mgPHA (as COD) mg removed substrates (as COD(-1)), respectively. When the substrate excess was present for more than 2 h (long-term batch tests), the storage rate and yield decreased, whereas growth rate and yield significantly increased due to biomass adaptation. A maximum polymer fraction in the biomass was therefore obtained at about 50% (on COD basis). As for the PHA composition, the copolymer poly(beta-hydroxybutyrate/beta-hydroxyvalerate) with 31% of hydroxyvalerate monomer was produced from the substrate mixture. Comparison of the tests with individual and mixed substrates seemed to indicate that, on removing the substrate mixture for copolymer production, propionic acid was fully utilized to produce propionylCoA, whereas the acetylCoA was fully provided by acetic and lactic acid.

Effect of periodic feeding in sequencing batch reactor on substrate uptake and storage rates by a pure culture of Amaricoccus kaplicensis.

A pure culture of Amaricoccus kaplicensis was aerobically cultured at a long culture residence time (Theta(C)>12d), under periodic acetate feeding in a sequencing batch reactor (SBR). The cycle length and, correspondingly, the volumetric organic load rate (vOLR) were varied in the range 4-24h and 0.76-0.12gCODl(-1)d(-1), respectively. The transient response of the microorganism to the acetate spike was investigated throughout batch tests, as a function of SBR cycle length and vOLR. In all tested conditions, a rapid transient response was observed, mainly due to acetate storage in the form of polyhydroxybutyrate, since growth (production of active biomass) played a minor role. Apart from this general trend, the maximum rates under transient conditions increased as the cycle length increased from 4 to 24h. In the SBR, the longest cycle also caused a decrease in floc size and settleability as well as an increase in the observed yield. The observed effect of SBR operating conditions on the physiological state of cells and their related transient response may have great significance on the performance of full scale activated sludge processes.