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.