The Use of Stable Zinc Isotope Soil Labeling to Assess the Contribution of Complex Organic Fertilizers to the Zinc Nutrition of Ryegrass

Manure and sewage sludge are known to add significant amounts of zinc (Zn) and other metals to soils. However, there is a paucity of information on the fate of Zn that derives from complex organic fertilizers in soil–plant systems and the contribution of these fertilizers to the Zn nutrition of crops. To answer these questions, we grew Italian ryegrass in the presence of ZnSO4, sewage sludge, and cattle and poultry manure in an acidic soil from Heitenried, Switzerland, and an alkaline soil from Strickhof, Switzerland, where the isotopically exchangeable Zn had been labeled with 67Zn. This allowed us to calculate the fraction of Zn in the shoots that was derived from fertilizer, soil, and seed over 4 successive cuts. In addition, we measured the 67Zn:66Zn isotope ratio with the diffusive gradients in thin films technique (DGT) on soils labeled with 67Zn and incubated with the same fertilizers. After 48 days of growth, the largest fraction of Zn in the ryegrass shoots was derived from the soil (79–88%), followed by the Zn-containing fertilizer (11–20%); the least (<2.3%) came from the seed. Only a minor fraction of the Zn applied with the fertilizer was transferred to the shoots (4.7–12%), which indicates that most of the freshly added Zn remained in the soil after one crop cycle and may thereby contribute to a residual Zn pool in the soil. The 67Zn:66Zn isotope ratios in the DGT extracts and the shoots measured at cut 4 were identical, suggesting that the DGT and plant took up Zn from the same pool. The proportion of Zn derived from the fertilizers in the DGT extracts was also identical to that measured in ryegrass shoots at cut 4. In conclusion, this work shows that stable Zn isotope labeling of the soil available Zn can be used to precisely quantify the impact of complex organic fertilizers on the Zn nutrition of crops. It also demonstrates that DGT extractions on labeled soils could be used to estimate the contribution of Zn fertilizers to plant nutrition.

Volatile depletion and evolution of Vesta from coupled Cu-Zn isotope systematics

<p>The moderately volatile elements, Cu and Zn, are not strongly affected by magmatic differentiation [1, 2] and are important tracers of volatile depletion in planetary bodies, particularly low-mass, airless bodies [3]. New isotopic ratio and abundance measurements for both Cu and Zn are presented for eucrites to more fully understand volatile depletion processes that affected the parent-body of the howardite-eucrite-diogenite (HED) meteorites, the asteroid 4-Vesta. Zinc isotope ratios are reported for twenty-eight eucrite samples, which along with prior data [4] yield a range of δ<sup>66</sup>Zn from -1.8 to +6.3 ‰, excluding one outlier, PCA 82502 (δ<sup>66</sup>Zn = -7.8 ‰) and a Zn concentration range from 0.3 to 3.8 p.p.m. Heavy Zn isotopic ratios (positive δ<sup>66</sup>Zn compositions) in eucrites form a negative trend with Zn concentration, reflecting volatile depletion processes on Vesta that are similar to the Moon [5, 6]. Within the combined sample set, eleven eucrites have light Zn isotopic compositions from δ<sup>66</sup>Zn of -0.02 to -7.8 ‰, with the majority having more negative compositions than likely chondritic precursors (maximum δ<sup>66</sup>Zn of ~ -0.2 ‰ [7]). These samples are interpreted to reflect condensates formed subsequent to surface volatilization and outgassing, such as during impact bombardment. Measurements of Cu compositions are also reported for nineteen of the samples, yielding a range of δ<sup>65</sup>Cu from -1.6 to +0.9 ‰, and range of Cu concentrations from 0.2 to 2.8 p.p.m., with the exception of Stannern (Cu > 10 ppm). As with Zn, negative Cu isotopic ratios that are lighter than chondritic compositions (δ<sup>65</sup>Cu ~ -0.5 ‰ [8]) are attributed to recondensation that occurred following impact-induced vaporization (cf. [9]). Within the wide ranges of Zn and Cu isotopic compositions measured in eucrites, most samples cluster within ~ 0 ‰ < δ<sup>66</sup>Zn < +3 ‰ and ~ 0.2 ‰ < δ<sup>65</sup>Cu < +0.9 ‰. This range is interpreted to reflect volatile depletion processes similar to those that affected the Moon (BSM: δ<sup>66</sup>Zn +1.4 ± 0.5‰ [5, 6, 10, 11] and δ<sup>65</sup>Cu = +0.92 ± 0.16‰ [9-11]). The greater heterogeneity in eucrite Zn and Cu isotopic compositions compared to lunar samples can be attributed to the smaller size of the HED parent asteroid, which may have experienced more limited homogenization of these signatures following volatile depletion and for eucrites which have experienced complex impact addition and metamorphic processes.  </p><p>[1] Chen et al. (2013) EPSL, 369, 34-42. [2] Savage et al. (2015) Geochemical Perspective Letters, 1, 53-64. [3] Day and Moynier (2014) Philisophical Transactions of the Royal Society A, 372, p.20130259. [4] Paniello et al. (2012) GCA, 86, 76-87. [5] Paniello et al. (2012) Nature, 490, 376-379. [6] Kato et al. 2015 Nature Communications, 6, 1-4. [7] Luck et al. (2005) GCA 69, 5351-5363. [8] Luck et al. (2003) GCA, 67¸143-151. [9] Day et al. (2019) GCA, 266, 131-143. [10] Moynier et al. (2006) GCA, 70, 6103-6117. [11] Herzog et al. (2009) GCA, 73, 5884-5904.</p>