Model Simulations on the Variability of Particulate MSA to Non-Sea-Salt Sulfate Ratio in the Marine Environment

A box model was constructed to investigate connections between the particulate MSA to non-sea-salt sulfate ratio, R, and DMS chemistry in a clean marine boundary layer. The simulations demonstrated that R varies widely with particle size, which must be taken into account when interpreting field measurements or comparing them with each other. In addition to DMS gas-phase chemistry, R in the submicron size range was shown to be sensitive to the factors dictating sulfate production via cloud processing, to the removal of SO₂ from the boundary layer by dry deposition and sea-salt oxidation, to the entrainment of SO₂ from the free troposphere, to the relative concentration of sub- and supermicron particles, and to meteorology. Three potential explanations for the increase of R toward high-latitudes during the summer were found: larger MSA yields from DMS oxidation at high latitudes, larger DMSO yields from DMS oxidation followed by the conversion of DMSO to MSA at high latitudes, or lower ambient H₂O₂ concentrations at high latitudes leading to less efficient sulfate production in clouds. Possible reasons for the large seasonal amplitude of R at mid and high latitudes include seasonal changes in the partitioning of DMS oxidation to the OH and NO₃ initiated pathways, seasonal changes in the concentration of species participating the DMS-OH reaction pathway, or the existence of a SO₂ source other than DMS oxidation in the marine boundary layer. Even small anthropogenic perturbations were shown to have a potential to alter the MSA to non-sea-salt sulfate ratio.     

Elemental and mineralogical changes in soils due to bioturbation along an earthworm invasion chronosequence in Northern Minnesota

Minnesota forested soils have evolved without the presence of earthworms since the last glacial retreat. When exotic earthworms arrive, enhanced soil bioturbation often results in dramatic morphological and chemical changes in soils with negative implications for the forests’ sustainability. However, the impacts of earthworm invasion on geochemical processes in soils are not well understood. This study attempts to quantify the role of earthworm invasion in mineral chemical weathering and nutrient dynamics along an earthworm invasion chronosequence in a sugar maple forest in Northern Minnesota. Depth and rates of soil mixing can be tracked with atmospherically derived short lived radioisotopes ²¹⁰Pb and ¹³⁷Cs. Their radioactivities increase in the lower A horizon at the expense of the peak activities near the soil surface, which indicate that soil mixing rate and its depth reach have been enhanced by earthworms. Enhanced soil mixing by earthworms is consistent with the ways that the vertical profiles of elemental and mineralogical compositions were affected by earthworm invasion. Biologically cycled Ca and P have peak concentrations near the soil surface prior to earthworm invasion. However, these peak abundances significantly declined in the earthworm invaded soils presumably due to enhanced soil mixing. It is clear that enhanced soil mixing due to earthworms also profoundly altered the vertical distribution of most mineral species within A horizons. Though the mechanisms are not clear yet, earthworm invasion appears to have contributed to net losses of clay mineral species and opal from the A horizons. As much as earthworms vertically relocated minerals and elements, they also intensify the contacts between organic matter and cations as shown in the increased amount of Ca and Fe in organically complexed and in exchangeable pools. With future studies on soil mixing rates and elemental leaching, this study will quantitatively and mechanically address the role of earthworms in geochemical evolution of soils and forests’ nutrient dynamics.     

Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.     

Preliminary model of nitrogen loads from southern bluefin tuna aquaculture

Farming of wild tuna in coastal areas is a relatively new aquaculture industry and little is known about the magnitude of nutrient discharges to the environment. In this work we present a preliminary model of nitrogen loads from southern bluefin tuna (Thunnus maccoyii) aquaculture in lower Spencer Gulf, South Australia. The model was developed based on feed inputs, estimates of fish metabolism and environmental data. Two pens were monitored over a full grow-out season to determine nitrogen sedimentation fluxes, remineralization at the sediment-water interface and accumulation in the sediments. The model suggests that the high metabolic rates of tuna lead to low retention of nitrogen in fish tissues (7-12% of feed inputs) and high environmental losses (260-502kg Ntonne(-1) growth). Considering Australian annual production of 4380tonnes over initial stocked biomass, total loads can reach 1137tonnes N per year, 86-92% lost as dissolved wastes. The nature of wastes suggests low localized impacts at current stocking densities and holding periods.     

A review of the physics and ecological implications of the thermal bar circulation

Following recent applications of numerical modelling and remote sensing to the thermal bar phenomenon, this paper seeks to review the current state of knowledge on the effect of its circulation on lacustrine plankton ecosystems. After summarising the literature on thermal bar hydrodynamics, a thorough review is made of all plankton observations taken in the presence of a thermal bar. Two distinct plankton growth regimes are found, one with production favoured throughout the inshore region and another with a maximum in plankton biomass near the position of the thermal bar. Possible explanations for the observed distributions are then discussed, with reference to numerical modelling studies, and the scope for future study of this interdisciplinary topic is outlined.     

Geophysical constraints on deep weathering and water storage potential in the Southern Sierra Critical Zone Observatory

The conversion of bedrock to regolith marks the inception of critical zone processes, but the factors that regulate it remain poorly understood. Although the thickness and degree of weathering of regolith are widely thought to be important regulators of the development of regolith and its water‐storage potential, the functional relationships between regolith properties and the processes that generate it remain poorly documented. This is due in part to the fact that regolith is difficult to characterize by direct observations over the broad scales needed for process‐based understanding of the critical zone. Here we use seismic refraction and resistivity imaging techniques to estimate variations in regolith thickness and porosity across a forested slope and swampy meadow in the Southern Sierra Critical Zone Observatory (SSCZO). Inferred seismic velocities and electrical resistivities image a weathering zone ranging in thickness from 10 to 35 m (average = 23 m) along one intensively studied transect. The inferred weathering zone consists of roughly equal thicknesses of saprolite (P‐velocity < 2 km s^?1) and moderately weathered bedrock (P‐velocity = 2–4 km s^?1). A minimum‐porosity model assuming dry pore space shows porosities as high as 50% near the surface, decreasing to near zero at the base of weathered rock. Physical properties of saprolite samples from hand augering and push cores are consistent with our rock physics model when variations in pore saturation are taken into account. Our results indicate that saprolite is a crucial reservoir of water, potentially storing an average of 3 m³ m^?2 of water along a forested slope in the headwaters of the SSCZO. When coupled with published erosion rates from cosmogenic nuclides, our geophysical estimates of weathering zone thickness imply regolith residence times on the order of 10⁵ years. Thus, soils at the surface today may integrate weathering over glacial–interglacial fluctuations in climate. Copyright © 2013 John Wiley & Sons, Ltd.     

A transport‐distance approach to scaling erosion rates: 1. Background and model development

The process basis of existing soil‐erosion models is shown to be ill‐founded. The existing literature builds directly or indirectly on Bennett's (1974) paper, which provided a blueprint for integrated catchment‐scale erosion modelling. Whereas Bennett recognized the inherent assumptions of the approach suggested, subsequent readings of the paper have led to a less critical approach. Most notably, the assumption that sediment movement could be approximated by a continuity equation that related to transport in suspension has produced a series of submodels that assume that all movement occurs in suspension. For commonly occurring conditions on hillslopes, this case is demonstrably untrue both on theoretical grounds and from empirical observations. Elsewhere in the catchment system, it is only partially true, and the extent to which the assumption is reasonable varies both spatially and temporally. A second ground‐breaking paper – that of Foster and Meyer (1972) – was responsible for subsequent uncritical application of a first‐order approximation to deposition based on steady‐state analysis and again a weak empirical basis. We describe in this paper an alternative model (Mahleran – Model for Assessing Hillslope‐Landscape Erosion, Runoff And Nutrients) based upon particle‐travel distance that overcomes existing limitations by incorporating parameterizations of the different detachment and transport mechanisms that occur in water erosion in hillslopes and small catchments. In the second paper in the series, we consider the sensitivity and general behaviour of Mahleran , and test it in relation to data from a large rainfall‐simulation experiment. The third paper of the sequence evaluates the model using data from plots of different sizes in monitored rainfall events. From this evaluation, we consider the scaling characteristics of the current form of Mahleran and suggest that integrated modelling, laboratory and field approaches are required in order to advance the state of the art in soil‐erosion modelling. Copyright © 2008 John Wiley & Sons, Ltd.