Negative emissions of carbon dioxide through chemical-looping combustion (CLC) and gasification (CLG) using oxygen carriers based on manganese and iron

Carbon capture and storage (CCS) is an economically attractive strategy for avoiding carbon dioxide (CO₂) emissions from, e.g., power plants to the atmosphere. The combination of CCS and biomass combustion would result in a reduction of atmospheric CO₂, or net negative emissions, as plant growth is a form of sequestration of atmospheric carbon. Carbon capture can be achieved in a variety of ways, one of which is chemical looping. Chemical-looping combustion (CLC) and chemical looping gasification (CLG) are two promising technologies for conversion of biomass to heat and power or syngas/methane with carbon capture. There have been significant advances made with respect to CLC in the last two decades for all types of fuel, with much less research on the gasification technology. CLG offers some interesting opportunities for production of biofuels together with carbon capture and may have several advantages with respect to the bench mark indirect gasification process or dual-bed fluidized bed (DFBG) in this respect. In CLG, an oxygen carrier is used as a bed material instead of sand, which is common in indirect gasification, and this could have several advantages: (i) all generated CO₂ is present together with the syngas or methane in the fuel reactor outlet stream, thus in a concentrated stream, viable for separation and capture; (ii) the air reactor (or combustion chamber) should largely be free from trace impurities, thus preventing corrosion and fouling in this reactor; and (iii) the highly oxidizing conditions in the fuel reactor together with solid oxide surfaces should be advantageous with respect to limiting formation of tar species. In this study, two manganese ores and an iron-based waste material, LD slag, were investigated with respect to performance in these chemical-looping technologies. The materials were also impregnated with alkali (K) in order to gauge possible catalytic effects and also to establish a better understanding of the general behavior of oxygen carriers with alkali, an important component in biomass and biomass waste streams and often a precursor for high-temperature corrosion. The viability of the oxygen carriers was investigated using a synthetic biogas in a batch fluidized bed reactor. The conversion of CO, H₂, CH₄, and C₂H₄ was investigated in the temperature interval 800–950 °C. The reactivity, or oxygen transfer rate, was highest for the manganese ores, followed by the LD slag. The conversion of C₂H₄ was generally high but could largely be attributed to thermal decomposition. The K-impregnated samples showed enhanced reactivity during combustion conditions, and the Mangagran-K sample was able to achieve full conversion of benzene. The interaction of the solid material with alkali showed widely different behavior. The two manganese ores retained almost all alkali after redox testing, albeit exhibiting different migration patterns inside the particles. LD slag lost most alkali to the gas phase during testing, although some remained, possibly explaining a small difference in reactivity. In summary, the CLC and CLG processes could clearly be interesting for production of heat, power, or biofuel with negative CO₂ emissions. Manganese ores are most promising from this study, as they could absorb alkali, giving a better conversion and perhaps also inhibiting or limiting corrosion mechanisms in a combustor or gasifier.

     

Phosphorus Flows to and from Swedish Agriculture and Food Chain

Phosphorus flows in Swedish agriculture and food chain were studied by material flow analysis. The system studied included agriculture, food consumption, related waste and wastewater from private households and municipal wastewater treatment plants. Swedish farmland had net annual phosphorus inputs of ~12 600 metric tons (4.1 kg P ha⁻¹) in 2008–2010. The total import of phosphorus in food and feed to Sweden exceed imports of phosphorus in fertilizers. Despite strict animal density regulations relating to manure phosphorus content, phosphorus is accumulating on Swedish animal farms. The total quantity of manure produced greatly exceeds imported mineral phosphorus fertilizer and almost equals total phosphorus inputs to Swedish farmland.     

Persistent organochlorine pollutants in children working at a waste-disposal site and in young females with high fish consumption in Managua, Nicaragua

The aim of this study was to assess persistent organochlorine pollutant (POP) levels in serum collected from children (11-15 years old) working and sometimes also living at the municipal waste-disposal site in Managua, located at the shore of Lake Managua, and in nonworking children living both nearby and also far away from the waste-disposal site. The influence of fish consumption was further evaluated by assessing POPs levels in serum from young women (15-24 years old) with markedly different patterns of fish consumption from Lake Managua. 2,2-bis(4-chlorophenyl)-1,1,1-trichloro-ethane (4,4'-DDT) and 2,2-bis(4-chlorophenyl)-1,1-dichloro-ethene (4,4'-DDE), gamma-hexachlorocyclohexane (gamma-HCH), polychlorinated biphenyls, pentachlorophenol, and polychlorobiphenylols were quantified in all samples. In general, the levels observed were higher than those reported in children from developed countries, such as Germany and United States. Toxaphene, aldrin, dieldrin, and beta-HCH could not be identified in any sample. The children working at the waste-disposal site had higher levels of POPs compared with the nonworking reference groups. In children not working, there were also gradients for several POPs, according to vicinity to the waste-disposal site. Moreover, in children, as well as in young women, there were gradients according to fish consumption. The most abundant component was 4,4'-DDE, but at levels still lower than those reported in children from malarious areas with a history of recent or current application of 4,4'-DDT for vector control.     

Maternal and cord serum exposure to PCB and DDE methyl sulfone metabolites in eastern Slovakia

Polychlorinated biphenyls (PCBs) were commercially produced between 1959 and 1984 in eastern Slovakia. Improper handling led to a highly contaminated local environment and high levels of PCBs in humans and wildlife in the Michalovce area. The aim of this study was to analyse serum for methylsulfonyl metabolites of PCB (MeSO(2)-PCBs) and DDE (3-MeSO(2)-DDE) in serum samples from pregnant women and in a selected number of paired cord blood samples to assess maternal sulfone levels and patterns, and transplacental transfer of these metabolites. The donating women were from two districts in eastern Slovakia. A liquid-liquid extraction method together with separation of substance groups and further clean-up on silica gel columns were applied prior to analysis by gas chromatography/mass spectrometry. 3-MeSO(2)-DDE was the major methyl sulfone in most of the samples followed by a yet not identified MeSO(2)-hexaCB, 4'-MeSO(2)-CB101, 4'-MeSO(2)-CB87 and 4-MeSO(2)-CB149. The women from the contaminated area had three times higher concentrations of the MeSO(2)-PCBs than women from the reference area. This is the first report on methyl sulfone metabolites of PCB and DDE in human cord serum. It is shown that these metabolites are transported through the placenta. The levels of MeSO(2)-PCBs in the maternal serum were about 1.5 times higher than in the corresponding cord serum on a lipid weight basis. For 3-MeSO(2)-DDE, the levels were about the same in maternal and cord serum. The difference in the maternal:cord ratio, comparing MeSO(2)-PCBs with 3-MeSO(2)-DDE might be due to differences in transport through the placenta caused by their different affinities for lipoproteins and plasma proteins.     

Avoiding CO2 capture effort and cost for negative CO2 emissions using industrial waste in chemical-looping combustion/gasification of biomass

Chemical-looping combustion (CLC) is a combustion process with inherent separation of carbon dioxide (CO₂), which is achieved by oxidizing the fuel with a solid oxygen carrier rather than with air. As fuel and combustion air are never mixed, no gas separation is necessary and, consequently, there is no direct cost or energy penalty for the separation of gases. The most common form of design of chemical-looping combustion systems uses circulating fluidized beds, which is an established and widely spread technology. Experiments were conducted in two different laboratory-scale CLC reactors with continuous fuel feeding and nominal fuel inputs of 300 W_th and 10 kW_th, respectively. As an oxygen carrier material, ground steel converter slag from the Linz–Donawitz process was used. This material is the second largest flow in an integrated steel mill and it is available in huge quantities, for which there is currently limited demand. Steel converter slag consists mainly of oxides of calcium (Ca), magnesium (Mg), iron (Fe), silicon (Si), and manganese (Mn). In the 300 W unit, chemical-looping combustion experiments were conducted with model fuels syngas (50 vol% hydrogen (H₂) in carbon monoxide (CO)) and methane (CH₄) at varied reactor temperature, fuel input, and oxygen-carrier circulation. Further, the ability of the oxygen-carrier material to release oxygen to the gas phase was investigated. In the 10 kW unit, the fuels used for combustion tests were steam-exploded pellets and wood char. The purpose of these experiments was to study more realistic biomass fuels and to assess the lifetime of the slag when employed as oxygen carrier. In addition, chemical-looping gasification was investigated in the 10 kW unit using both steam-exploded pellets and regular wood pellets as fuels. In the 300 W unit, up to 99.9% of syngas conversion was achieved at 280 kg/MW_th and 900 °C, while the highest conversion achieved with methane was 60% at 280 kg/MW_th and 950 °C. The material’s ability to release oxygen to the gas phase, i.e., CLOU property, was developed during the initial hours with fuel operation and the activated material released 1–2 vol% of O₂ into a flow of argon between 850 and 950 °C. The material’s initial low density decreased somewhat during CLC operation. In the 10 kW, CO₂ yields of 75–82% were achieved with all three fuels tested in CLC conditions, while carbon leakage was very low in most cases, i.e., below 1%. With wood char as fuel, at a fuel input of 1.8 kW_th, a CO₂ yield of 92% could be achieved. The carbon fraction of C₂-species was usually below 2.5% and no C₃-species were detected. During chemical-looping gasification investigation a raw gas was produced that contained mostly H₂. The oxygen carrier lifetime was estimated to be about 110–170 h. However, due to its high availability and potentially low cost, this type of slag could be suitable for large-scale operation. The study also includes a discussion on the potential advantages of this technology over other technologies available for Bio-Energy Carbon Capture and Storage, BECCS. Furthermore, the paper calls for the use of adequate policy instruments to foster the development of this kind of technologies, with great potential for cost reduction but presently without commercial application because of lack of incentives.

     

Environmental exposure to POPs and heavy metals in urban children from Dhaka, Bangladesh

Persistent organic pollutants (POPs) and heavy metals are well known environmental pollutants. Even though numerous studies have been carried out to assess human exposures to these compounds, there is still a lack of data on humans from developing countries, especially in underprivileged children. The objective of this study was to assess the exposure to POPs and heavy metals in children from Dhaka, Bangladesh. One specific aim was to investigate whether children working at, or living close to, open waste disposal sites (WDSs) were more heavily exposed than other urban children. In 2008, blood and serum were collected from 73 children aged 7-16 from five neighbourhoods. Some of the children lived and worked at WDSs (N = 31), others lived next to a WDS (N = 17), whereas some children lived far from such sites (N = 25). Blood levels of lead (B-Pb), cadmium (B-Cd), and selenium (B-Se) were determined by ICP-MS for all subjects. The metal levels were high, with B-Pb overall mean 120 μg L(-1) (range 40-220), B-Cd 0.74 μg L(-1) (0.22-4.1), and B-Se 120 μg L(-1) (81-170). There were no marked differences between children from the different neighbourhoods, or between WDS workers and other children. PCB levels were low and with no contrast between neighbourhoods, for CB-153 the overall mean was 7.0 ng g(-1) fat (2.8-51). In contrast, high levels of DDTs were observed in all children, for 4,4'-DDE 1300 ng g(-1) fat (420-4600), and for 4,4'-DDT 326 ng g(-1) fat (44-1400), indicating ongoing exposure. PBDE levels were low, and BDE-209 was quantitated mainly in children working at or living close to WDSs. In conclusion, the high levels of DDTs, lead and cadmium observed in children from Dhaka are of concern. Many children were exposed at levels where health effects have been observed, or at levels without safety margins.     

Applying the dark diversity concept to nature conservation

Linking diversity to biological processes is central for developing informed and effective conservation decisions. Unfortunately, observable patterns provide only a proportion of the information necessary for fully understanding the mechanisms and processes acting on a particular population or community. We suggest conservation managers use the often overlooked information relative to species absences and pay particular attention to dark diversity (i.e., a set of species that are absent from a site but that could disperse to and establish there, in other words, the absent portion of a habitat‐specific species pool). Together with existing ecological metrics, concepts, and conservation tools, dark diversity can be used to complement and further develop conservation prioritization and management decisions through an understanding of biodiversity relativized by its potential (i.e., its species pool). Furthermore, through a detailed understanding of the population, community, and functional dark diversity, the restoration potential of degraded habitats can be more rigorously assessed and so to the likelihood of successful species invasions. We suggest the application of the dark diversity concept is currently an underappreciated source of information that is valuable for conservation applications ranging from macroscale conservation prioritization to more locally scaled restoration ecology and the management of invasive species.     

Agriculture as Provider of Both Food and Fuel

A database of global agricultural primary production has been constructed and used to estimate its energy content. The portion of crops available for food and biofuel after postharvest losses was evaluated. The basic conditions for agriculture and plant growth were studied, to ensure sustainable scenarios regarding use of residues. The available energy contents for the world and EU27 was found to be 7,200–9,300 and 430 TWh, respectively, to be compared with food requirements of 7,100 and 530 TWh. Clearly, very little, or nothing, remains for biofuel from agricultural primary crops. However, by using residues and bioorganic waste, it was found that biofuel production could theoretically replace one-fourth of the global consumption of fossil fuels for transport. The expansion potential for global agriculture is limited by availability of land, water, and energy. A future decrease in supply of fossil energy and ongoing land degradation will thus cause difficulties for increased biofuel production from agriculture.     

Placental transfer of polychlorinated biphenyls, their hydroxylated metabolites and pentachlorophenol in pregnant women from eastern Slovakia

The aim of the present study was to understand the placental transfer of polychlorinated biphenyls (PCBs), specific hydroxylated PCB metabolites (OH-PCBs), and pentachlorophenol (PCP) in blood serum, in a birth cohort from eastern Slovakia. During the period 2002-2004, cord blood specimens were collected in parallel with maternal specimens from women delivering in the two eastern Slovak districts of Michalovce and Svidnik/Stropkov. A total of 92 pairs of mother-cord specimens at delivery were selected for this study. 4-OH-CB107, 3-OH-CB153, 4-OH-CB146, 3'-OH-CB138, 4-OH-CB187, and 4'-OH-CB172 were quantified. The median concentrations of Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP in cord serum were 0.92, 0.33, and 0.69 ng/g wet wt., respectively and highly correlated with the corresponding maternal serum levels (correlations were R(2)=0.61, 0.78, and 0.82, respectively). The median cord to mother ratios of the Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP were 0.18, 0.75, and 1.10, respectively. The median ratio of the Sigma(6)OH-PCBs to the Sigma(17) PCBs in the cord serum was 0.38 from wet weight based concentrations, which was about four times higher than the ratio of these compounds in maternal serum (0.09). PCP was more abundant than any PCB or OH-PCB congener measured in cord serum. The higher cord to maternal ratios of OH-PCB metabolites as compared with the parent compounds suggests either a higher placental transfer rate or greater metabolism in the fetus as compared with the maternal compartment. These findings are consistent with their preferential binding to TTR that can cross the placenta. The cord to maternal ratio varies by congener (e.g., 4-OH-CB107=0.58, 4-OH-CB146=0.74, 3'-OH-CB138=1.01).     

160 h of chemical-looping combustion in a 10 kW reactor system with a NiO-based oxygen carrier

Chemical-looping combustion, CLC, is a technology with inherent separation of the greenhouse gas CO₂. The technique uses an oxygen carrier made up of particulate metal oxide to transfer oxygen from combustion air to fuel. In this work, an oxygen carrier consisting of 60% NiO and 40% NiAl₂O₄ was used in a 10 kW CLC reactor system for 160 h of operation with fuel. The first 3 h of fuel operation excepted, the test series was accomplished with the same batch of oxygen carrier particles. The fuel used in the experiments was natural gas, and a fuel conversion to CO₂ of approximately 99% was accomplished. Combustion conditions were very stable during the test period, except for the operation at sub-stoichiometric conditions. It was shown that the methane fraction in the fuel reactor exit gas was dependent upon the rate of solids circulation, with higher circulation leading to more unconverted methane. The carbon monoxide fraction was found to follow the thermodynamical equilibrium for all investigated fuel reactor temperatures, 660–950 °C. Thermal analysis of the fuel reactor at stable conditions enabled calculation of the particle circulation which was found to be approximately 4 kg/s, MW. The loss of fines, i.e. the amount of elutriated oxygen carrier particles with diameter <45 μm, decreased during the entire test period. After 160 h of operation the fractional loss of fines was 0.00022 h⁻¹, corresponding to a particle life time of 4500 h.