Ecosystem services in vineyard landscapes: a focus on aboveground carbon storage and accumulation.

BACKGROUND: Organic viticulture can generate a range of ecosystem services including supporting biodiversity, reducing the use of conventional pesticides and fertilizers, and mitigating greenhouse gas emissions through long-term carbon (C) storage. Here we focused on aboveground C storage rates and accumulation using a one-year increment analysis applied across different winegrape varietals and different-aged vineyard blocks. This produced a chronosequence of C storage rates over what is roughly the productive lifespan of most vines (aged 2-30 years). To our knowledge, this study provides the first estimate of C storage rates in the woody biomass of vines. Additionally, we assessed C storage in wildland buffers and adjacent oak-dominated habitats over a 9-year period. RESULTS: Carbon storage averaged 6.5 Mg/Ha in vines. We found the average annual increase in woody C storage was 43% by mass. Variation correlated most strongly with vine age, where the younger the vine, the greater the relative increase in annual C. Decreases in C increment rates with vine age were more than offset by the greater overall biomass of older vines, such that C on the landscape continued to increase over the life of the vines at 18.5% per year on average. Varietal did not significantly affect storage rates or total C stored. Carbon storage averaged 81.7 Mg/Ha in native perennial buffer vegetation; we found an 11% increase in mass over 9 years for oak woodlands and savannas. CONCLUSIONS: Despite a decrease in the annual rate of C accumulation as vines age, we found a net increase in aboveground C in the woody biomass of vines. The results indicate the positive role that older vines play in on-farm (vineyard) C and overall aboveground accumulation rates. Additionally, we found that the conservation of native perennial vegetation as vineyard buffers and edge habitats contributes substantially to overall C stores. We recommend that future research consider longer time horizons for increment analysis, as this should improve the precision of C accumulation rate estimates, including in belowground (i.e., soil) reservoirs.

Strong temporal and spatial variation of dissolved Cu isotope composition in acid mine drainage under contrasted hydrological conditions.

Copper export and mobility in acid mine drainage are difficult to understand with conventional approaches. Within this context, Cu isotopes could be a powerful tool and here we have examined the relative abundance of dissolved (<0.22 µm) Cu isotopes (δ65Cu) in the Meca River which is an outlet of the Tharsis mine, one of the largest abandoned mines of the Iberian Pyrite Belt, Spain. We followed the chemical and isotopic composition of the upstream and downstream points of the catchment during a 24-h diel cycle. Additional δ65Cu values were obtained from the tributary stream, suspended matter (>0.22 µm) and bed sediments samples. Our goals were to 1) assess Cu sources variability at the upstream point under contrasted hydrological conditions and 2) investigate the conservative vs. non conservative Cu behavior along a stream. Average δ65Cu values varied from -0.47 to -0.08‰ (n = 9) upstream and from -0.63 to -0.31‰ downstream (n = 7) demonstrating that Cu isotopes are heterogeneous over the diel cycle and along the Meca River. During dry conditions, at the upstream point of the Meca River the Cu isotopic composition was heavier which is in agreement with the preferential release of heavy isotopes during the oxidative dissolution of primary sulfides. The more negative values obtained during high water flow are explained by the contribution of soil and waste deposit weathering. Finally, a comparison of upstream vs. downstream Cu isotope composition is consistent with a conservative behavior of Cu, and isotope mass balance calculations estimate that 87% of dissolved Cu detected downstream originate from the Tharsis mine outlet. These interpretations were supported by thermodynamic modelling and sediment characterization data (X-ray diffraction, Raman Spectroscopy). Overall, based on contrasted hydrological conditions (dry vs flooded), and taking the advantage of isotope insensitivity to dilution, the present work demonstrates the efficiency of using the Cu isotopes approach for tracing sources and processes in the AMD regions.

Zinc stable isotope fractionation during its adsorption on oxides and hydroxides.

Adsorption of Zn on goethite, hematite, birnessite, pyrolusite, corundum, and gibbsite was studied using a batch adsorption technique as a function of pH, zinc concentration in solution, and time of exposure. Adsorption from 0.01 M NaNO3 solutions undersaturated with respect to zinc (hydr)oxide at 3MeOZn+ complexes, where Me=Fe, Mn, and Al, was used to describe the dependence of adsorption equilibria on aqueous solution composition in a wide range of pH and Zn concentration. The logarithms of surface stability constant for Zn interaction with metal oxy(hydr)oxides (>MeOH0+Zn2+-->MeOZn+) vary from -2.5 to 0.5. They are higher for oxy(hydr)oxides than for anhydrous oxides. Stable isotopes of zinc in several filtrates were measured using an ICP-MS Neptune multicollector which made it possible, for the first time, to assess the degree of isotopic fractionation between 66Zn and 64Zn during zinc adsorption on mineral surfaces. The isotopic offset between aqueous solution and mineral surfaces (Delta(66/64)Zn(soln/solid)=delta((66/64)Zn)(solution)-delta((66/64)Zn)(surface)) was found to be weakly dependent on percentage of adsorbed metal and equals 0.20+/-0.03, 0.17+/-0.06, -0.10+/-0.03, -0.10+/-0.09, and -0.13+/-0.12 per thousand for goethite, birnessite, pyrolusite, corundum, and Al(OH)3. For hematite, Delta(66/64)Zn varies from -0.61+/-0.10 per thousand at pH 5.5 to -0.02+/-0.09 per thousand at 5.8MeOZn(H2O)(n) complexes (available literature data on X-ray absorption spectroscopy). Apparently, the fine structure of surface complexes and the position and bond strength for second neighbors of zinc are likely to control its isotopic fractionation during adsorption on mineral surfaces. Our results strongly suggest that inorganic processes controlling zinc isotope adsorption on soil and sediment minerals should be of second-order importance compared to biological factors.

Kinetic steric factors and connectivity indices.

In this study the relationships between previously reported connectivity indices described by Kier and Hall and steric contributions to the rate constants for several series of reactions are examined. Rate data were examined for four different series of reactions, which were chosen to represent a range of different reaction mechanisms and transition-state structures. For sterically controlled reactions, the relative rates of series of substrates can be correlated either with the connectivity indices of the substrates themselves or with the changes in the indices that accompany formation of transition states. As expected, the significant indices in the correlations are of the cluster and path-cluster types. The connectivity indices should be useful descriptors in helping relate equilibrium properties, chemical reactivities, and pharmacological data to one another.

Origin and fate of copper in a small Mediterranean vineyard catchment: new insights from combined chemical extraction and δ65Cu isotopic composition.

For centuries, many Mediterranean catchments were covered with vineyards in which copper was widely applied to protect grapevines against fungus. In the Mediterranean-type flow regime, brief and intense flood events increase the stream water discharge by up to 10 times and cause soil leaching and storm runoff. Because vineyards are primarily cultivated on steep slopes, high Cu fluxes are discharged by surface water runoff into the rivers. The purpose of this work was to investigate the riverine behavior and transport of anthropogenic Cu by coupling a sequential chemical extraction (SCE) procedure, used to determine Cu partitioning between residual and non-residual fractions, with δ(65)Cu isotopic measurements in each fraction. In the Baillaury catchment, France, we sampled soils (cultivated and abandoned), river bed sediments (BS), suspended particulate matter (SPM), and river water during the flash flood event of February 2009. Copper partitioning using SCE show that most of Cu in abandoned vineyard soil was in the residual phase (>60%) whereas in cultivated soil, BS and SPM, Cu was mostly (>25%) in non-residual fractions, mainly adsorbed onto iron oxide fractions. A small fraction of Cu was associated with organic matter (5 to 10%). Calculated enrichment factors (EF) are higher than 2 and the anthropogenic contribution was estimated between 50 to 85%. Values for δ(65)Cu in bulk samples were similar to bedrock therefore; δ(65)Cu on SCE fractions of superficial soils and SPM allowed for discrimination between Cu origin and distribution. Copper in residual fractions was of natural mineral origin (δ(65)Cu close to local bedrock, +0.07‰). Copper in water soluble fraction of SPM (δ(65)Cu=+0.26‰) was similar to dissolved river Cu (δ(65)Cu=+0.31‰). Copper from fungicide treatment (δ(65)Cu=-0.35‰) was bound to organic matter (δ(65)Cu=-0.20‰) without or with slight isotopic fractioning. A preferential adsorption of (65)Cu onto iron oxides (δ(65)Cu=+0.5‰) is shown.