Mikrostrukturierte Sensoren für die pH-Wert-Bestimung auf Basis von dünnen, intrinisch leitfähigen Polyanilinschichten

Der pH-Wert stellt in der Chemie, Physik, Biologie, Pharmazie und Medizin eine wichtige Meßgröße dar, da eine Vielzahl von Reaktionen durch den pH-Wert bestimmt wird. In der Regel werden zur pH-Wert-Messung Glaselektroden eingesetzt. Hierbei konnte der pH-sensitive Bereich zwar bis auf einige Mikrometer reduziert werden, aber die Gesamtab-messungen betragen immer noch 15-20 cm. Mit der Einführung miniaturisierter Reaktionsgefäße ist daher der Bedarf an miniaturisierten Sensoren enorm gestiegen. Um in solchen Gefäßen Reaktionsparameter wie z. B. den pH-Wert zu kontrollieren, müssen die Gesamtabmessungen der Sensoren verringert werden. Dies lässt sich mit Hilfe der Mikrostrukturtechnik von Silizium realisieren. Hiermit lassen sich Strukturen und ganze Systeme bis in den Nanometerbereich herstellen. Basierend auf Silizium und Gold als Elektrodenmaterial wurden im Rahmen dieser Arbeit verschiedene Interdigitalstrukturen hergestellt. Um diese Strukturen zur pH-Wert-Messungen einsetzen zu können, müssen sie mit einer pH-sensitiven Schicht versehen werden. Hierbei wurde Polyanilin, ein intrinsisch leitendes Polymer, aufgrund seine pH-abhängigen elektrischen und optischen Verhaltens eingesetzt. Die Beschichtung dieser Sensoren mit Polyanilin erfolgte vorwiegend elektrochemisch mit Hilfe der Zyklovoltammetrie. Neben der Herstellung reiner Polyanilinfilme wurden auch Kopolymerisationen von Anilin und seinen entsprechenden Aminobenzoesäure- bzw. Aminobenzensulfonsäurederivaten durchgeführt. Ergebnisse dazu werden vorgestellt und diskutiert. Zur Charakterisierung der resultierenden Polyanilin- und Kopolymerfilme auf den Inter-digitalstrukturen wurden mit Hilfe der ATR-FT-IR-Spektroskopie Spektren aufgenommen, die gezeigt und diskutiert werden. Eine elektrochemische Charakterisierung der Polymere erfolgte mittels der Zyklovoltammetrie. Die mit Polyanilin bzw. seinen Kopolymeren beschichteten Sensoren wurden dann für Widerstandsmessungen an den Polymerfilmen in wässrigen Medien eingesetzt. Polyanilin zeigt lediglich eine pH-Sensitivität in einem pH-Bereich von pH 2 bis pH 4. Durch den Einsatz der Kopolymere konnte dieser pH-sensitive Bereich jedoch bis zu einem pH-Wert von 10 ausgeweitet werden. Zur weiteren Miniaturisierung der Sensoren wurde das Konzept der interdigitalen Elektroden-paare auf Cantilever übertragen. Die pH-sensitive Zone konnte dabei auf 500 µm2 bei einer Gesamtlänge des Sensors (Halter mit integriertem Cantilever) von 4 mm reduziert werden. Neben den elektrischen pH-abhängigen Eigenschaften können auch die optischen Eigen-schaften des Polyanilins zur pH-Detektion herangezogen werden. Diese wurden zunächst mit Hilfe der UV-VIS-Spektroskopie untersucht. Die erhaltenen Spektren werden gezeigt und kurz diskutiert. Mit Hilfe eines Raster-Sonden-Mikroskops (a-SNOM, Firma WITec) wurden Reflexionsmessungen an Polyanilinschichten durchgeführt. Zur weiteren Miniaturisierung wurden Siliziumdioxidhohlpyramiden (Basisfläche 400 µm2) mit Spitzenöffnungen in einem Bereich von 50-150 nm mit Polyanilin beschichtet. Auch hier sollten die optischen Eigenschaften des Polyanilins zur pH-Wert-Sensorik ausgenutzt werden. Es werden erste Messungen an diesen Strukturen in Transmission diskutiert.

Root-induced increases in soil pH and nutrient availability to field-grown cereals and legumes on acid sandy soils of Sudano-Sahelian West Africa

A field experiment with millet (Pennisetum glaucum L.), sorghum [Sorghum bicolor (L.) Moench], cowpea (Vigna unguiculata L.) and groundnut (Arachnis hypogeae L.) was conducted on severely P-deficient acid sandy soils of Niger, Mali and Burkina Faso to measure changes in pH and nutrient availability as affected by distance from the root surface and by mineral fertiliser application. Treatments included three rates of phosphorus (P) and four levels of nitrogen (N) application. Bulk, rhizosphere and rhizoplane soils were sampled at 35, 45 and 75 DAS in 1997 and at 55 and 65 DAS in 1998. Regardless of the cropping system and level of mineral fertiliser applied, soil pH consistently increased between 0.7 and two units from the bulk soil to the rhizoplane of millet. Similar pH gradients were observed in cowpea, but pH changes were much smaller in sorghum with a difference of only 0.3 units. Shifts in pH led to large increases in nutrient availability close to the roots. Compared with the bulk soil, available P in the rhizoplane was between 190 and 270% higher for P-Bray and between 360 and 600% higher for P-water. Exchangeable calcium (Ca) and magnesium (Mg) levels were also higher in the millet rhizoplane than in the bulk soil, whereas exchangeable aluminium (Al) levels decreased with increasing pH close to the root surface. The results suggest an important role of root-induced pH increases for crops to cope with acidity-induced nutrient deficiency and Al stress of soils in the Sudano-Sahelian zone of West Africa.

Nutrient cycling and field-based partial nutrient balances in two mountain oases of Oman

Little is known about nutrient fluxes as a criterion to assess the sustainability of traditional irrigation agriculture in eastern Arabia. In this study GIS-based field research on terraced cropland and groves of date palm (Phoenix dactylifera L.) was conducted over 2 years in two mountain oases of northern Oman to determine their role as hypothesized sinks for nitrogen (N), phosphorus (P) and potassium (K). At Balad Seet 55% of the 385 fields received annual inputs of 100–500 kg N ha^-1 and 26% received 500–1400 kg N ha^-1. No N was applied to 19% of the fields which were under fallow. Phosphorus was applied annually at 1–90 kg ha^-1 on 46% of the fields, whereas 27% received 90–210 kg ha^-1. No K was applied to 27% of the fields, 32% received 1–300 kg K ha^-1, and the remaining fields received up to 1400 kg ha^-1. At Maqta N-inputs were 61–277 kg ha^-1 in palm groves and 112–225 kg ha^-1 in wheat (Triticum spp.) fields, respective P inputs were 9–40 and 14–29 kg ha^-1, and K inputs were 98–421 and 113–227 kg ha^-1. For cropland, partial oasis balances (comprising inputs of manure, mineral fertilizers, N2-fixation and irrigation water, and outputs of harvested products) were similar for both oases, with per hectare surpluses of 131 kg N, 37 kg P, and 84 kg K at Balad Seet and of 136 kg N, 16 kg P and 66 kg K at Maqta. This was despite the fact that N2-fixation by alfalfa (Medicago sativa L.), estimated at up to 480 kg ha^-1 yr^-1 with an average total dry matter of 22 t ha^-1, contributed to the cropland N-balance only at the former site. Respective palm grove surpluses, in contrast were with 303 kg N, 38 kg P, and 173 kg K ha^-1 much higher at Balad Seet than with 84 kg N, 14 kg P, and 91 kg K ha^-1 at Maqta. The data show that both oases presently are large sinks for nutrients. Potential gaseous and leaching losses could at least partly be controlled by a decrease in nutrient input intensity and careful incorporation of manure.

Plant genetic diversity, irrigation and nutrient cycling in traditional mountain oases of northern Oman

Little is known about plant biodiversity, irrigation management and nutrient fluxes as criteria to assess the sustainability of traditional irrigation agriculture in eastern Arabia. Therefore interdisciplinary studies were conducted over 4 yrs on flood-irrigated fields dominated by wheat (Triticum spp.), alfalfa (Medicago sativa L.) and date palm (Phoenix dactylifera L.) in two mountain oases of northern Oman. In both oases wheat landraces consisted of varietal mixtures comprising T. aestivum and T. durum of which at least two botanical varieties were new to science. During irrigation cycles of 6-9 days on an alfalfa-planted soil, volumetric water contents ranged from 30-13%. For cropland, partial oasis balances (comprising inputs of manure, mineral fertilizers, N2-fixation and irrigation water, and outputs of harvested products) were similar for both oases, with per hectare annual surpluses of 131 kg N, 37 kg P and 84 kg K at Balad Seet and of 136 kg N, 16 kg P and 66 kg K at Maqta. Respective palm grove surpluses, in contrast were with 303 kg N, 38 kg P, and 173 kg K ha^-1 yr^-1 much higher at Balad Seet than with 84 kg N, 14 kg P and 91 kg K ha^-1 yr^-1 at Maqta. The results show that the sustainability of these irrigated landuse systems depends on a high quality of the irrigation water with low Na but high CaCO3, intensive recycling of manure and an elaborate terrace structure with a well tailored water management system that allows adequate drainage.

Pharmaceutical consumption and residuals potentially relevant to nutrient cycling in Greater Accra, Ghana

Recycling nutrients form sanitary wastes back into agricultural ecosystems offers an option to alleviate soil depletion in regions where the use of mineral fertiliser is limited. Exemplary nutrient and water cycling approaches, including collection, treatment and use of human urine, are established at Valley View University (VVU) in Greater Accra, Ghana. Concerns have been recently raised in regard to fate and impact of pharmaceutical residues in soils and interlinked environment. To evaluate in how far emerging knowledge can be transposed onto VVU, urban and rural environments in Greater Accra, spatial disease occurrence and drug consumption patterns were studied. Malaria has been found to represent the most severe health burden in Ghana, but there is also a high prevalence of infectious diseases. Drugs consumed in great quantities and in respect to their residual loads potentially problematic in the environment belong to therapeutic groups of: antibiotics, analgesics, drugs for diabetes, antimalarials, cardiovascular drugs and anthelmintics. Drug consumption revealed to be highest in urban and lowest in rural areas. At VVU the range of consumed drugs is comparable to urban areas except for the negligible use of diabetes and cardiovascular medication as well as contraceptives.

Nutrient cycling and nutrient use efficiency in urban and peri-urban agriculture of Kabul, Afghanistan

Like elsewhere also in Kabul, Afghanistan urban and peri-urban agriculture (UPA) has often been accused of being resource inefficient and unsustainable causing negatives externalities to community health and to the surroundings. These arise from the inappropriate management and use of agricultural inputs, including often pesticides and inter-city wastes containing heavy metal residues and pathogens. To address these concerns, parallel studies with the aims of quantification of carbon (C), nitrogen (N), phosphorus (P) and potassium (K) horizontal and vertical fluxes; the assessment of heavy metal and pathogen contaminations of UPA produce, and an economic analysis of cereal, vegetable and grape production systems conducted for two years in UPA of Kabul from April 2008 to October 2009. The results of the studies from these three UPA diverse production systems can be abridged as follows: Biennial net balances in vegetable production systems were positive for N (80 kg ha-1 ), P (75 kg ha-1) and C (3,927 kg ha-1), negative for K (-205 kg ha-1), whereas in cereal production systems biennial horizontal balances were positive for P (20 kg ha-1 ) and C (4,900 kg ha-1) negative for N (-155 kg ha-1) and K (-355 kg ha-1) and in vineyards corresponding values were highly positive for N (295 kg ha-1), P (235 kg ha-1), C (3,362 kg ha-1) and slightly positive for K (5 kg ha-1). Regardless of N and C gaseous emissions, yearly leaching losses of N and P in selected vegetable gardens varied from 70 - 205 kg N ha-1 and 5 - 10 kg P ha-1. Manure and irrigation water contributed on average 12 - 79% to total Inputs of N, P, K and C, 10 - 53% to total inputs of C in the gardens and fields. The elevated levels of heavy metal and pathogen loads on fresh UPA vegetables reflected contamination from increasing traffic in the city, deposits of the past decades of war, lacking collection and treatment of raw inter-city wastes which call for solutions to protect consumer and producer health and increase reliability of UPA productions. A cost-revenue analysis of all inputs and outputs of cereal, vegetable and grapes production systems over two years showed substantial differences in net UPA household income. To confirm these results, more detailed studies are needed, but tailoring and managing the optimal application of inputs to crop needs will significantly enhance farmer’s better revenues as will as environmental and produce quality.

Short-term effects of human urine fertiliser and wood ash on soil pH and electrical conductivity

The fertiliser value of human urine has been examined on several crops, yet little is known about its effects on key soil properties of agronomic significance. This study investigated temporal soil salinization potential of human urine fertiliser (HUF). It further looked at combined effects of human urine and wood ash (WA) on soil pH, urine-NH_3 volatilisation, soil electrical conductivity (EC), and basic cation contents of two Acrisols (Adenta and Toje series) from the coastal savannah zone of Ghana. The experiment was a factorial design conducted in the laboratory for 12 weeks. The results indicated an increase in soil pH by 1.2 units for Adenta series and 1 unit for Toje series after one week of HUF application followed by a decline by about 2 pH units for both soil types after twelve weeks. This was attributed to nitrification of ammonium to nitrate leading to acidification. The EC otherwise increased with HUF application creating slightly saline conditions in Toje series and non-saline conditions in Adenta series. When WA was applied with HUF, both soil pH and EC increased. In contrast, the HUF alone slightly salinized Toje series, but both soils remained non-saline whenWA and HUF were applied together. The application ofWA resulted in two-fold increase in Ca, Mg, K, and Na content compared to HUF alone. Hence, WA is a promising amendment of acid soils and could reduce the effect of soluble salts in human urine fertilizer, which is likely to cause soil salinity.