[1] The dynamics of biologic Si cycling in grassland ecosystems are largely unknown and likely to impact mineral weathering rates regionally and diatom productivity globally; key regulatory processes in the global Si cycle are closely tied to the global carbon cycle. Across a bioclimatic sequence spanning major grassland ecosystems in the Great Plains, soil biogenic silica depth distributions are similar to that of soil organic carbon; however, unlike soil organic carbon, quantities of soil biogenic silica decrease with increasing precipitation, despite an increase in annual biogenic inputs through litterfall across the same gradient. Though comprising only 1-3% of the total Si pool, faster turnover of biogenic Si and annual cycling by grasses should positively impact mineral dissolution. Our results suggest that the largest reservoir of biogenic Si in terrestrial ecosystems resides in soils, and emphasize the potential significance of grasslands in the global biogeochemical cycle of Si.

SummaryMany studies have highlighted the importance of the Amorphous Silica (ASi) pool to the overall mass balance in the biogeosphere. In order to advance our knowledge of measurements and quantification of this pool, it is necessary to compare the ability of different extractants to dissolve ASi in soils and to test methods developed in the aquatic sciences to soils systems. The methods used in this work included three acid extraction techniques (0.2 M NH 4 -oxalate, 0.1 M NH 4 -citrate and 0.5 M NH 4 -acetate) and two alkaline extraction techniques (0.094 M Na 2 CO 3 and 0.5 M NaOH), which are more commonly used for the measurement of ASi in aquatic sediments. Our results indicate that the amount of Si extracted from phytolith samples with the acid methods was two orders of magnitude less than the amount of extracted by alkaline extractions. When applied to natural soil samples, these extractions show that the acid techniques are only able to extract loosely-bound components such as adsorbed Si and Si bound in amorphous matrices with Al and Fe. While Na 2 CO 3 or NaOH extracted the same amount of ASi in Podzols, Na 2 CO 3 was able to extract only part of the ASi extracted with NaOH in Chernozems. Pretreatment of the samples with 0.1 M HCl before the Na 2 CO 3 extraction did not increase amounts of ASi extracted. The present work suggests that alkaline methods used commonly for ASi on aquatic sediment samples can be used on a wide variety of soils.

Slight differences in the chemical behavior of germanium (Ge) and silicon (Si) during soil weathering enable Ge/Si ratios to be used as a tracer of Si pathways. Mineral weathering and biogenic silicon cycling are the primary modifiers of Ge/Si ratios, but knowledge of the biogenic cycling component is based on relatively few studies. We conducted two sets of greenhouse experiments in order to better quantify the range and variability in Ge discrimination by plants. Graminoid species commonly found in North American grassland systems, Agropyron smithii, Schizachyrium scoparium, and Andropogon gerardii were grown under controlled hydroponic environmental conditions. Silicon leaf contents were positively correlated with solution Si and ambient temperature but not with nutrient solution pH, electrical conductivity, or species. The Ge/Si ratio incorporated into phytoliths shows a distribution coefficient [(Ge/Si) phytolith /(Ge/Si) solution ] of about 0.2 and is remarkably invariant between species, photosynthetic pathway, and solution temperature. Ge seems to be discriminated against during the uptake and translocation of Si to the opal deposition sites by about a factor of five. In the second experiment, a wider range of graminoid species (Agropyron smithii, Bouteloua gracilis, Buchloe dactyloides, Oryzopsis hymenoides, Schizachyrium scoparium and Andropogon gerardii) were grown in two different soil mediums. Plant phytoliths showed a distribution factor of about 0.4 for field grown grasses, and 0.6 for potting soil grown grasses with no clear trends among the species. Evidence of the direction and degree of biological Ge discrimination during plant uptake provides a geochemical finger print for plants and improves the utility of Ge/Si ratios in studies of terrestrial weathering and links between Si cycles in terrestrial and marine systems.

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