A new particulate Mn-Fe-P-shuttle at the redoxcline of anoxic basins

Pelagic redoxclines of anoxic basins and deeps form the suboxic transition between oxygenated surface and anoxic or even sulfidic bottom waters. Intense element cycling, favoured by elevated microbial activity, causes steep gradients of physico-chemical parameters, nutrients and redox-sensitive trace metals. This study presents a conceptual model for authigenic particle formation at pelagic redoxclines, which is based on the tight coupling of Mn, Fe, and P cycles. Besides the well-known occurrence of Mn-oxides, textural (SEM-EDX) and geochemical (ICP-OES, ICP-MS) analyses of particles from the redoxclines of the Black Sea and the Baltic Sea (Gotland Basin, Landsort Deep) evidence the existence of earlier postulated Fe-oxyhydroxo-phosphates and emphasize mixed phases consisting of Mn-oxides and Fe-oxyhydroxo-phosphates as a new solid species. Most of the analyzed particles are star-shaped, of about 5 μm in size, and occur as single particles or aggregates without any morphological differences between Mn-oxides, Fe-oxyhydroxo-phosphates, and mixed phases. Throughout the redoxcline, these minerals show a general succession with maximum abundance of Mn-oxides above the redoxcline followed by mixed phases and almost pure Fe-phosphates within and below the redoxcline, respectively. Molar Fe/P ratios of single particles argue against the formation of known pure Fe-phosphates like vivianite or strengite at the lower end of the redox transition zone, but are consistent with recent experimental findings for colloidal P-bearing hydrous ferric oxides. Moreover, morphological similarities suggest the formation of irregular Fe-oxyhydroxo coatings due to oxidation of upward diffusing Fe²⁺ by oxygen and stepwise replacement of Mn(IV) by Fe(III) on sinking MnO_x particles followed by immediate adsorption or even co-precipitation of phosphate. Batch-type experiments using biogenic MnO_x particles demonstrate the efficient potential of Fe²⁺ oxidation by sinking MnO_x particles. When entering sulfidic waters MnO_x particles are progressively reduced leading to an increasing relative abundance of Fe- and P-rich particles. In deeper parts of the water column these particles are also reductively dissolved, thereby releasing Fe²⁺ and phosphate to the water column. This Mn-Fe-P-shuttle likely affects phosphate transport throughout the water column and thus impacts primary production at least over longer time scales. Furthermore, the particulate Mn-Fe-P-shuttle must have played an important role for the cycling of P and certain trace metals in ancient ocean basins, e.g., during certain periods of Cretaceous black shale formation and should be considered in future mass balances and modeling approaches dealing with oxic/anoxic interfaces of aquatic ecosystems.     

Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity

Emissions of volatile organic compounds (VOCs) from sunflower (Helianthus annuus L. cv. giganteus) were measured in a continuously stirred tank reactor. The compounds predominantly emitted from sunflower were: isoprene, the monoterpenes -pinene, -pinene, sabinene, 3-carene and limonene, an oxygenated terpene, not positively identified so far and the sesquiterpene -caryophyllene. Emission rates ranged from 0.8 x 10^–16 to 4.3 x 10 ^–15 mol cm^–2 s^–1 at a temperature of 25°C and at a light intensity of 820 µEm^–2 s^–1. A dependence of the emission rates on temperature as well as on light intensity was observed. The emission rates of -pinene, sabinene and thujene from beech (Fagus sylvatica L.) were also affected by temperature as well as by light intensity. Our results suggest that an emission algorithm for all compounds emitted from sunflower and beech has to consider temperature and light intensity simultaneously. The observations strongly indicate that the emissions of VOCs from sunflower and beech are in part closely coupled to the rate of biosynthesis and in part originate from diffusion out of pools. The emission rates can be described by an algorithm that combines the model given by Tingey and coworkers with the algorithm given by Guenther and coworkers after slight modification.     

A laser-photolysis fragment-fluorescence (LPFF) method for the detection of gaseous nitric acid in ambient air

The development and first tests of a novel method for the direct, sensitive, selective, and fast detection of gaseous nitric acid in air are described. The detection method is based on the laser-photolysis fragment-fluorescence (LPFF) method using 193 nm (ArF) laser light. The photolysis process yielding OH fluorescence has been thoroughly investigated. Up to now, the method has been found to be practically free of interferences. The mixing ratio for nitric acid is measured on-line with a detection limit of about 0.1 ppbv for an accumulation time of the signal of 10–15 min. A number of tests and field measurements were performed to demonstrate the feasibility and limits of the described detection method.     

Field verification of a theoretical model to predict the dynamic response of a soft clay deposit

A 40-m thick clay deposit was subjected to sinusoidal excitations using a foundation block and an eccentric mass type vibrator. The response of the foundation block and the surrounding soil was measured using geophones inside the soil and on the surface. The phase shift between the excitation signal and the response signal, the accelerations of the foundation block and the particle velocities in the soil are compared with those obtained from a frequency-dependent numerical model based on the exact analytical solution for the boundary value problem of a rectangular foundation resting on a linear elastic halfspace.     

Rainfall-triggering response patterns of post-seismic debris flows in the Wenchuan earthquake area

Several giant debris flows occurred in southwestern China after the Wenchuan earthquake, causing serious casualties and economic losses. Debris flows were frequently triggered after the earthquake. A relatively accurate prediction of these post-seismic debris flows can help to reduce the consequent damages. Existing debris flow prediction is almost based on the study of the relationship between post-earthquake debris flows and rainfall. The relationship between the occurrence of post-seismic debris flows and characteristic rainfall patterns was studied in this paper. Fourteen rainfall events related to debris flows that occurred in four watersheds in the Wenchuan earthquake area were collected. By analyzing the rainfall data, characteristics of rainfall events that triggered debris flows after the earthquake were obtained. Both the critical maximum rainfall intensity and average rainfall intensity increased with the time. To describe the critical conditions for debris flow initiation, intensity–duration curves were constructed, which shows how the threshold for triggering debris flows increased each year. The time that the critical rainfall intensities of debris flow occurrences return to the value prior to the earthquake could not be estimated due to the absent rainfall data before the earthquake. Rainfall-triggering response patterns could be distinguished for rainfall-induced debris flows. The critical rainfall patterns related to debris flows could be divided on the basis of antecedent rainfall duration and intensity into three categories: (1) a rapid triggering response pattern, (2) an intermediate triggering response pattern, and (3) a slow triggering response pattern. The triggering response patterns are closely related to the initiation mechanisms of post-earthquake debris flows. The main difference in initiation mechanisms and difference in triggering patterns by rainfall is regulated by the infiltration process and determined by a number of parameters, such as hydro-mechanical soil characteristics, the thickness of the soil, and the slope gradient. In case of a rapid triggering response rainfall pattern, the hydraulic conductivity and initial moisture content are the main impact factors. Runoff erosion and rapid loading of solid material is the dominant process. In case of a rainfall pattern with a slow triggering response, the thickness and strength of the soil, high hydraulic conductivity, and rainfall intensity are the impact factors. Probably slope failure is the most dominant process initiating debris flows. In case of an intermediate triggering response pattern, both debris flow initiation mechanisms (runoff erosion and slope failure) can play a role.     

Temperature of cometary dust

The variation of the dust temperature with heliocentric distance for a comet is calculated using the optical constants of an astronomically important silicate.