| Calcium (Ca) is an essential macronutrient that is increasingly recognized as a biogeochemical factor that influences ecosystem structure and function. Progress in understanding the sustainability of ecosystem Ca supply has been hampered by a lack of information on the various forms and pools of Ca in forest ecosystems. In particular, few studies have investigated the role of Ca-oxalate (Ca-ox), a ubiquitous and sparingly soluble biomineral formed by plants and fungi, on Ca cycling. I investigated Ca-ox pools in two young Douglas-fir forests in the Oregon Coast Range, and found that Ca-ox comprised 4 to 18% of total ecosystem Ca in high- and low-Ca sites, respectively, with roughly even distribution in vegetation, detritus and mineral soil to 1 m depth. The proportion of ecosystem Ca existing as Ca-ox varied by ecosystem compartment but was highest in needle litterfall, foliage and branches. Calcium-ox could be a large amount of Ca in mineral soil; across nine sites comprising a local soil Ca gradient, we found as much as 20% of available Ca in 0–10 cm depth mineral soil occurs as Ca-ox. Ca-ox was the dominant form of Ca returned from plants to soil, but disappeared as rapidly as bulk Ca from decomposing litter, suggesting an important pathway for Ca recycling. In mineral soil, Ca-ox was a larger portion of total available Ca in the low-Ca site, which had lower Ca-ox concentrations overall, suggesting that Ca-ox has limited potential to buffer against Ca depletion in forests where Ca is in shortest supply. I investigated foliar chemistry as a method for diagnosis of nutrient deficiencies in high and low-Ca sites where Ca varied inversely with soil nitrogen (N), and which had received fertilization with urea (for nitrogen, N), lime, and calcium chloride three years prior. Foliar vector diagrams suggested N limitation at the low-N site and N sufficiency at the high-N site, but did not suggest Ca deficiency at either site after urea, lime and Ca-chloride fertilization. The high-Ca site displayed 20–60 times higher concentrations of foliar Ca-oxalate than the low-Ca site, although this was unaffected by fertilization. Soil nitrification responded to both N and lime fertilization at both sites, suggesting that fertilization with N may stimulate nitrification that could accelerate soil Ca loss. I also investigated how Ca-ox may influence cation tracers such as Ca and strontium (Sr) ratios (i.e., Ca/Sr) and Ca-isotopes (44Ca/40Ca), which are used to identify sources and pathways of Ca cycling in ecosystem studies. Laboratory synthesis of Ca-ox crystals exhibited preference for Ca over Sr, and for 40Ca over 44Ca. In the field, discrimination between Ca and Sr was detected in bulk plant tissues due to Ca-ox accumulation, suggesting that Ca-ox accumulation related to tree Ca supply status could influence interpretations of Ca/Sr as a tracer of Ca cycling. I also found that standard methods of soil exchangeable Ca extraction could dissolve Ca-ox crystals and potentially contribute an additional 52% to standard measurements of exchangeable-Ca pools in low-Ca sites, thus complicating long-standing interpretations of available soil Ca pools and dynamics in many studies. Results of this work show overall that Ca-ox is found in large quantities in plants, detritus, and mineral soil in forest ecosystems, and is a more dynamic component of ecosystem Ca cycling than previously recognized. |
