Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

Natural perchlorate (ClO₄⁻) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ³⁷Cl, δ¹⁸O, and Δ¹⁷O), indicating that ClO₄⁻ may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO₄⁻, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO₄⁻ in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO₄⁻ was transported from solutions into plants similarly to NO₃⁻ but preferentially to Cl⁻ (4-fold). The ClO₄⁻ isotopic compositions of initial ClO₄⁻ reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO₄⁻ uptake or accumulation. The ClO₄⁻ isotopic composition of field-grown snap beans was also consistent with that of ClO₄⁻ in varying proportions from irrigation water and precipitation. NO₃⁻ uptake had little or no effect on NO₃⁻ isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (¹⁵N/¹⁸O) ratio of 1.05 was observed between NO₃⁻ in hydroponic solutions and leaf extracts, consistent with partial NO₃⁻ reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO₄⁻ in commercial produce, as illustrated by spinach, for which the ClO₄⁻ isotopic composition was similar to that of indigenous natural ClO₄⁻. Our results indicate that some types of plants can accumulate and (presumably) release ClO₄⁻ to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO₄⁻ and NO₃⁻ in plants may be useful for determining sources of fertilizers and sources of ClO₄⁻ in their growth environments and consequently in food supplies. - Highlights: • Methods were developed to extract perchlorate from plants for isotopic analysis. • Perchlorate and nitrate entered bean plants with little or no isotopic fractionation. • Nitrate was fractionated isotopically within plants, whereas perchlorate was not. • Data provided no evidence that plants cause isotopic variation of natural perchlorate. • Perchlorate and nitrate isotopes in vegetables may reflect fertilizer and irrigation sources.