Zur Reaktionskinetik der Oxidation von Kohlenstoffmaterialien aus Biomasse

Zur Modellierung von Vergasungs- und Verbrennungsprozessen zur energetischen Nutzung von Biomasse ist die Kenntnis von reaktionskinetischen Daten für die Sauerstoff-Oxidation von Biomassepyrolysaten erforderlich. Eine ausführliche Literaturübersicht zeigt den Stand der Forschung bezüglich der experimentellen Ermittlung von reaktionskinetischen Parametern für die Oxidation von Pyrolysaten aus Lignin, Cellulose und pflanzlicher Biomasse sowie der Suche nach einem plausiblen Reaktionsmechanismus für die Reaktion von Sauerstoff mit festen Kohlenstoffmaterialien. Es wird eine Versuchsanlage mit einem quasistationär betriebenen Differentialreaktor konstruiert, die eine Messung der Reaktionskinetik und der reaktiven inneren Oberfläche (RSA) für die Reaktion eines Pyrolysats aus Maispflanzen mit Sauerstoff ermöglicht. Die getrockneten und zerkleinerten Maispflanzen werden 7 Minuten lang bei 1073 K in einem Drehrohrofen pyrolysiert. Das Pyrolysat zeichnet sich vor allem durch seine hohe Porosität von über 0,9 und seinen hohen Aschegehalt von 0,24 aus. Die RSA wird nach der Methode der Messung von Übergangskinetiken (TK) bestimmt. Die Bestimmung der RSA erfolgt für die Reaktionsprodukte CO und CO2 getrennt, für die entsprechend ermittelten Werte werden die Bezeichnungen CO-RSA und CO2-RSA eingeführt. Die Abhängigkeit dieser Größen von der Sauerstoffkonzentration läßt sich durch eine Langmuir-Isotherme beschreiben, ebenso das leichte Absinken der CO-RSA mit der Kohlendioxidkonzentration. Über dem Abbrand zeigen sich unterschiedliche Verläufe für die CO-RSA, CO2-RSA und die innere Oberfläche nach der BET-Methode. Zur Charakterisierung der Oberflächenzwischenprodukte werden temperaturprogrammierte Desorptionsversuche (TPD) durchgeführt. Die Ergebnisse zeigen, daß eine Unterscheidung in zwei Kohlenstoff-Sauerstoff-Oberflächenkomplexe ausreichend ist. Die experimentellen Untersuchungen zum Oxidationsverlauf werden im kinetisch bestimmten Bereich durchgeführt. Dabei werden die Parameter Temperatur, Sauerstoff-, CO- und CO2-Konzentration variiert. Anhand der Ergebnisse der reaktionskinetischen Untersuchungen wird ein Reaktionsmechanismus für die Kohlenstoff-Sauerstoff-Reaktion entwickelt. Dieser Reaktionsmechanismus umfaßt 7 Elementarreaktionen, für welche die reaktionskinetischen Parameter numerisch ermittelt werden. Darüber hinaus werden reaktionskinetische Parameter für einfachere massenbezogene Reaktionsgeschwindigkeitsansätze berechnet und summarische Reaktionsgeschwindigkeitsansätze für die Bildung von CO und CO2 aus dem Reaktionsmechanismus hergeleitet.

Microbial use of organic substrates and maize growth, especially in saline and alkaline soils of Pakistani Punjab

This thesis consists of 4 main parts: (1) impact of growing maize on the decomposition of incorporated fresh alfalfa residues, (2) relationships between soil biological and other soil properties in saline and alkaline arable soils from the Pakistani Punjab, (3) decomposition of compost and plant residues in Pakistani soils along a gradient in salinity, and (4) interactions of compost and triple superphosphate on the growth of maize in a saline Pakistani soil. These 4 chapters are framed by a General Introduction and a Conclusions section. (1) In the first study, the effects of growing maize plants on the microbial decomposition of freshly chopped alfalfa residues was investigated in a 90-day pot experiment using a sandy arable soil. Assuming that the addition of alfalfa residues did not affect the decomposition of native soil organic matter, only 27% of the alfalfa residues were found as CO2. This suggests that a considerable part of alfalfa-C remained undecomposed in the soil. However, only 6% of the alfalfa residues could be recovered as plant remains in treatment with solely alfalfa residues. Based on d13C values, it was calculated that plant remains in treatment maize + alfalfa residues contained 14.7% alfalfa residues and 85.3% maize root remains. This means 60% more alfalfa-C was recovered in this treatment. (2) In the second study, the interactions between soil physical, soil chemical and soil biological properties were analysed in 30 Pakistani soils from alkaline and saline arable sites differing strongly in salinisation and in soil pH. The soil biological properties were differentiated into indices for microbial activity, microbial biomass, and community structure with the aim of assessing their potential as soil fertility indices. (3) In the third study, 3 organic amendments (compost, maize straw and pea straw) were added to 5 Pakistani soils from a gradient in salinity. Although salinity has depressive effects on microbial biomass C, biomass N, biomass P, and ergosterol, the clear gradient according to the soil salt concentration was not reflected by the soil microbial properties. The addition of the 3 organic amendments always increased the contents of the microbial indices analysed. The amendment-induced increase was especially strong for microbial biomass P and reflected the total P content of the added substrates. (4) The fourth study was greenhouse pot experiment with different combinations of compost and triple superphosphate amendments to investigate the interactions between plant growth, microbial biomass formation and compost decomposition in a strongly saline Pakistani arable soil in comparison to a non-saline German arable soil. The Pakistani soil had a 2 times lower content of ergosterol, a 4 times lower contents of microbial biomass C, biomass N and biomass P, but nearly a 20 times lower content of NaHCO3 extractable P. The addition of 1% compost always had positive effects on the microbial properties and also on the content of NaHCO3 extractable P. The addition of superphosphate induced a strong and similar absolute increase in microbial biomass P in both soils.

Produktion und Nutzung von mikrobiellen Residuen als labile Zwischenspeicher für Nährstoffe

Mit dem Ziel, die Bildung und den Verbrauch von mikrobiellen Residuen zu ermitteln, wurden zwei Inkubationsversuche durchgeführt. Die Versuchsdauer betrug jeweils 67 Tage, wobei an den Tagen 5, 12, 33, 38, 45 und 67 Proben entnommen und auf Ct, Cmik, CO2 sowie die δ13C-Werte, Nt, Nmin und Ergosterol untersucht wurden. In Versuch 1 wurden als leicht umsetzbare Kohlenstoffquelle 3 mg C4-Kohlenstoff g-1Boden in Form von Rohrzucker bzw. Maiscellulose und als N-Ausgleich 200 µg NH4NO3-N g-1Boden hinzugegeben. Der verwendete Boden war ein Lößboden. In Versuch 2 wurden 3 mg C4-Kohlenstoff g-1Boden in Form von Rohrzucker und 100 µg NH4NO3-N g-1Boden in den Boden eingearbeitet. Als Substrat wurde hier ein gebrannter Lößboden verwendet. Bei beiden Versuchen erfolgte an Tag 33 nochmals eine Zugabe von 3 mg C3-Kohlenstoff g-1Boden in Form von Cellulose. Die Zugabe des C4-Kohlenstoffs führte in beiden Versuchen zu einer Zunahme des C4-Anteils in der mikrobiellen Biomasse. Insgesamt wurden im ersten Versuch ca. 78 % des C4-Kohlenstoffs und im zweiten Versuch ca. 64 % mineralisiert. In Versuch 1 wurde bei der Rohrzuckervariante der größte Teil an C4-C innerhalb der ersten 5 Tage mineralisiert, in der Cellulosevariante konnte dagegen eine geringere, aber länger anhaltende Mineralisation bis Tag 33 beobachtet werden. Dies sowie die Entwicklung des C4-C der mikrobiellen Biomasse deuten darauf hin, dass die Cellulose erst zu diesem Zeitpunkt vollständig umgesetzt war, der Rohrzucker dagegen aber schon nach 5 Inkubationstagen. Der Anteil an C4-C in den mikrobiellen Residuen lag an Tag 33 bei 28 % (Cellulosevariante) bzw. 22 % (Rohrzuckervariante) des zugegebenen C4-Kohlenstoffs. Dagegen lag im zweiten Versuch der Anteil an C4-Kohlenstoff in den mikrobiellen Residuen bei 40 %. In Versuch 1 führte die Zugabe der C3-Cellulose an Tag 33 nicht zu einem Verbrauch von mikrobiellen Residuen, im Versuch 2 hingegen zu einer signifikanten Abnahme. Der zugegebene Stickstoff wurde in beiden Versuchen durch die Zugabe des Rohrzuckers in hohen Anteilen immobilisiert, aber nur in geringem Umfang in die mikrobielle Biomasse inkorporiert. An Tag 33 lag der Anteil Stickstoff in den mikrobiellen Residuen bei 52 % (Versuch 1) bzw. 84 % (Versuch 2) des zugegebenen Stickstoffs. In Versuch 1 setzte nach 33 Tagen eine Remineralisation des immobilisierten Stickstoffs ein, unabhängig von der Zugabe der C3-Cellulose. In Versuch 2 wurde der immobilisierte Stickstoff zu keinem Zeitpunkt remineralisiert. Die Zugabe der C3-Cellulose führte hier nicht zu einer Remineralisation des immobilisierten Stickstoffs. Es bestätigte sich die Annahme, dass durch die Zugabe von leicht umsetzbaren Kohlstoffsubstraten die Bildung von mikrobiellen Residuen gesteigert werden kann. Die zweite Annahme, dass durch die Zugabe von N-freiem Substrat, hier C3-Cellulose, die mikrobiellen Residuen bevorzugt abgebaut werden, konnte nicht bestätigt werden.

Field measurements of the CO2 evolution rate under different crops during an irrigation cycle in a mountain oasis of Oman

For millennia oasis agriculture has been the backbone of rural livelihood in the desertic Sultanate of Oman. However, little is known about the functioning of these oasis systems, in particular with respect to the C turnover. The objective was to determine the effects of crop, i.e. alfalfa, wheat and bare fallow on the CO2 evolution rate during an irrigation cycle in relation to changes in soil water content and soil temperature. The gravimetric soil water content decreased from initially 24% to approximately 16% within 7 days after irrigation. The mean CO2 evolution rates increased significantly in the order fallow (27.4 mg C m^−2 h^−1) < wheat (45.5 mg C m^−2 h^−1) < alfalfa (97.5 mg C m^−2 h^−1). It can be calculated from these data that the CO2 evolution rate of the alfalfa root system was nearly four times higher than the corresponding rate in the wheat root system. The decline in CO2 evolution rate, especially during the first 4 days after irrigation, was significantly related to the decline in the gravimetric water content, with r = 0.70. CO2 evolution rate and soil temperature at 5 cm depth were negatively correlated (r = -0.56,n = 261) due to increasing soil temperature with decreasing gravimetric water content.

Salinity-induced changes in the microbial use of sugarcane filter cake added to soil

Five laboratory incubation experiments were carried out to assess the salinity-induced changes in the microbial use of sugarcane filter cake added to soil. The first laboratory experiment was carried out to prove the hypothesis that the lower content of fungal biomass in a saline soil reduces the decomposition of a complex organic substrate in comparison to a non-saline soil under acidic conditions. Three different rates (0.5, 1.0, and 2.0%) of sugarcane filter cake were added to both soils and incubated for 63 days at 30°C. In the saline control soil without amendment, cumulative CO2 production was 70% greater than in the corresponding non-saline control soil, but the formation of inorganic N did not differ between these two soils. However, nitrification was inhibited in the saline soil. The increase in cumulative CO2 production by adding filter cake was similar in both soils, corresponding to 29% of the filter cake C at all three addition rates. Also the increases in microbial biomass C and biomass N were linearly related to the amount of filter cake added, but this increase was slightly higher for both properties in the saline soil. In contrast to microbial biomass, the absolute increase in ergosterol content in the saline soil was on average only half that in the non-saline soil and it showed also strong temporal changes during the incubation: A strong initial increase after adding the filter cake was followed by a rapid decline. The addition of filter cake led to immobilisation of inorganic N in both soils. This immobilisation was not expected, because the total C-to-total N ratio of the filter cake was below 13 and the organic C-to-organic N ratio in the 0.5 M K2SO4 extract of this material was even lower at 9.2. The immobilisation was considerably higher in the saline soil than in the non-saline soil. The N immobilisation capacity of sugarcane filter cake should be considered when this material is applied to arable sites at high rations. The second incubation experiment was carried out to examine the N immobilizing effect of sugarcane filter cake (C/N ratio of 12.4) and to investigate whether mixing it with compost (C/N ratio of 10.5) has any synergistic effects on C and N mineralization after incorporation into the soil. Approximately 19% of the compost C added and 37% of the filter cake C were evolved as CO2, assuming that the amendments had no effects on the decomposition of soil organic C. However, only 28% of the added filter cake was lost according to the total C and d13C values. Filter cake and compost contained initially significant concentrations of inorganic N, which was nearly completely immobilized between day 7 and 14 of the incubation in most cases. After day 14, N re-mineralization occurred at an average rate of 0.73 µg N g-1 soil d-1 in most amendment treatments, paralleling the N mineralization rate of the non-amended control without significant difference. No significant net N mineralization from the amendment N occurred in any of the amendment treatments in comparison to the control. The addition of compost and filter cake resulted in a linear increase in microbial biomass C with increasing amounts of C added. This increase was not affected by differences in substrate quality, especially the three times larger content of K2SO4 extractable organic C in the sugarcane filter cake. In most amendment treatments, microbial biomass C and biomass N increased until the end of the incubation. No synergistic effects could be observed in the mixture treatments of compost and sugarcane filter cake. The third 42-day incubation experiment was conducted to answer the questions whether the decomposition of sugarcane filter cake also result in immobilization of nitrogen in a saline alkaline soil and whether the mixing of sugarcane filter cake with glucose (adjusted to a C/N ratio of 12.5 with (NH4)2SO4) change its decomposition. The relative percentage CO2 evolved increased from 35% of the added C in the pure 0.5% filter cake treatment to 41% in the 0.5% filter cake +0.25% glucose treatment to 48% in the 0.5% filter cake +0.5% glucose treatment. The three different amendment treatments led to immediate increases in microbial biomass C and biomass N within 6 h that persisted only in the pure filter cake treatment until the end of the incubation. The fungal cell-membrane component ergosterol showed initially an over-proportionate increase in relation to microbial biomass C that fully disappeared at the end of the incubation. The cellulase activity showed a 5-fold increase after filter cake addition, which was not further increased by the additional glucose amendment. The cellulase activity showed an exponential decline to values around 4% of the initial value in all treatments. The amount of inorganic N immobilized from day 0 to day 14 increased with increasing amount of C added in comparison to the control treatment. Since day 14, the immobilized N was re-mineralized at rates between 1.31 and 1.51 µg N g-1 soil d-1 in the amendment treatments and was thus more than doubled in comparison with the control treatment. This means that the re-mineralization rate is independent from the actual size of the microbial residues pool and also independent from the size of the soil microbial biomass. Other unknown soil properties seem to form a soil-specific gate for the release of inorganic N. The fourth incubation experiment was carried out with the objective of assessing the effects of salt additions containing different anions (Cl-, SO42-, HCO3-) on the microbial use of sugarcane filter cake and dhancha leaves amended to inoculated sterile quartz sand. In the subsequent fifth experiment, the objective was to assess the effects of inoculum and temperature on the decomposition of sugar cane filter cake. In the fourth experiment, sugarcane filter cake led to significantly lower respiration rates, lower contents of extractable C and N, and lower contents of microbial biomass C and N than dhancha leaves, but to a higher respiratory quotient RQ and to a higher content of the fungal biomarker ergosterol. The RQ was significantly increased after salt addition, when comparing the average of all salinity treatments with the control. Differences in anion composition had no clear effects on the RQ values. In experiment 2, the rise in temperature from 20 to 40°C increased the CO2 production rate by a factor of 1.6, the O2 consumption rate by a factor of 1.9 and the ergosterol content by 60%. In contrast, the contents of microbial biomass N decreased by 60% and the RQ by 13%. The effects of the inoculation with a saline soil were in most cases negative and did not indicate a better adaptation of these organisms to salinity. The general effects of anion composition on microbial biomass and activity indices were small and inconsistent. Only the fraction of 0.5 M K2SO4 extractable C and N in non-fumigated soil was consistently increased in the 1.2 M NaHCO3 treatment of both experiments. In contrast to the small salinity effects, the quality of the substrate has overwhelming effects on microbial biomass and activity indices, especially on the fungal part of the microbial community.

Effects of Organic and Inorganic Fertilizers on Growth and Yield of Banana (Musa AAA cv. Malindi) in Oman

The Sultanate of Oman is located on the south-eastern coast of the Arabian Peninsula, which lies on the south-western tip of the Asian continent. The strategic geographical locations of the Sultanate with its many maritime ports distributed on the Indian Ocean have historically made it one of the Arabian Peninsula leaders in the international maritime trade sector. Intensive trading relationships over long time periods have contributed to the high plant diversity seen in Oman where agricultural production depends entirely on irrigation from groundwater sources. As a consequence of the expansion of the irrigated area, groundwater depletion has increased, leading to the intrusion of seawater into freshwater aquifers. This phenomenon has caused water and soil salinity problems in large parts of the Al-Batinah governorate of Oman and threatens cultivated crops, including banana (Musa spp.). According to the Ministry of Agriculture and Fisheries, the majority of South Al-Batinah farms are affected by salinity (ECe > 4 dS m-1). As no alternative farmland is available, the reclamation of salt-affected soils using simple cultural practices is of paramount importance, but in Oman little scientific research has been conducted to develop such methods of reclamation. This doctoral study was initiated to help filling this research gap, particularly for bananas. A literature review of the banana cultivation history revealed that the banana germplasm on the Arabian Peninsula is probably introduced from Indonesia and India via maritime routes across the Indian Ocean and the Red Sea. In a second part of this dissertation, two experiments are described. A laboratory trial conducted at the University of Kassel, in Witzenhausen, Germany from June to July 2010. This incubation experiment was done to explore how C and N mineralization of composted dairy manure and date palm straw differed in alkaline non-saline and saline soils. Each soil was amended with four organic fertilizers: 1) composted dairy manure, 2) manure + 10% date palm straw, 3) manure + 30% date palm straw or 4) date palm straw alone, in addition to un-amended soils as control. The results showed that the saline soil had a lower soil organic C content and microbial biomass C than the non-saline soil. This led to lower mineralization rates of manure and date palm straw in the saline soil. In the non-saline soil, the application of manure and straw resulted in significant increases of CO2 emissions, equivalent to 2.5 and 30% of the added C, respectively. In the non-amended control treatment of the saline soil, the sum of CO2-C reached only 55% of the soil organic C in comparison with the non-saline soil. In which 66% of the added manure and 75% of the added straw were emitted, assuming that no interactions occurred between soil organic C, manure C and straw C during microbial decomposition. The application of straw always led to a net N immobilization compared to the control. Salinity had no specific effect on N mineralization as indicated by the CO2-C to Nmin ratio of soil organic matter and manure. However, N immobilization was markedly stronger in the saline soil. Date palm straw strongly promoted saprotrophic fungi in contrast to manure and the combined application of manure and date palm straw had synergistic positive effects on soil microorganisms. In the last week of incubation, net-N mineralization was observed in nearly all treatments. The strongest increase in microbial biomass C was observed in the manure + straw treatment. In both soils, manure had no effect on the fungi-specific membrane component ergosterol. In contrast, the application of straw resulted in strong increases of the ergosterol content. A field experiment was conducted on two adjacent fields at the Agricultural Research Station, Rumais (23°41’15” N, 57°59’1” E) in the South of Al-Batinah Plain in Oman from October 2007 to July 2009. In this experiment, the effects of 24 soil and fertilizer treatments on the growth and productivity of Musa AAA cv. 'Malindi' were evaluated. The treatments consisted of two soil types (saline and amended non-saline), two fertilizer application methods (mixed and ring applied), six fertilizer amendments (1: fresh dairy manure, 2: composted dairy manure, 3: composted dairy manure and 10% date palm straw, 4: composted dairy manure and 30% date palm straw, 5: only NPK, and 6: NPK and micronutrients). Sandy loam soil was imported from another part of Oman to amended the soil in the planting holes and create non-saline conditions in the root-zone. The results indicate that replacing the saline soil in the root zone by non-saline soil improved plant growth and yield more than fertilizer amendments or application methods. Particularly those plants on amended soil where NPK was applied using the ring method and which received micronutrients grew significantly faster to harvest (339 days), had a higher average bunch weight (9.5 kg/bunch) and were consequently more productive (10.6 tonnes/hectare/cycle) compared to the other treatments.