Assessment of rapid low-cost isotope (δ15 N, δ18 O) analyses of nitrate in fruit extracts by Ti(III) reduction to differentiate organic from conventional production.

RATIONALE: The isotopic composition (δ15 N, δ18 O) of nitrate in fruits and vegetables differentiates organic from conventional food production practices. Organic systems do not use synthetic nitrate fertilizers high in 18 O and low in 15 N and thereby help reveal producers' fertilization claims. Isotope analyses of nitrate extracted from fruits and vegetables are done by bacterial reduction which is costly and by specialized laboratories. Rapid, low-cost methods are needed to promulgate nitrate isotope analyses of food products to support organic food product certification and to verify the authenticity of production claims. METHODS: Fresh strawberry samples were obtained from certified organic and conventional growers in Andalucía, Spain. We applied a new, rapid, one-step Ti(III) reduction method to convert the nitrate from strawberry extracts to N2 O gas for headspace isotope analyses using isotope-ratio mass spectrometry. Using the Ti(III) reduction method, 70 samples, controls and references were prepared and analyzed for NO3 - , δ15 N and δ18 O per 48 h. We also analyzed extracts and solids for anions and cations and for bulk δ15 N for multivariate chemometric evaluation. RESULTS: The Ti(III)-based isotope analyses of nitrate in strawberry extracts revealed clear differentiation between organic and conventional production with mean δ18 O and δ15 N values of +18.3 ± 1.2 ‰ and +17.6 ± 1.2 ‰ versus +28.2 ± 4.5 ‰ and +14.9 ± 3.0 ‰, respectively. The δ15 N of strawberry dry mass differed slightly (+3.0 ± 1.4 ‰ versus +4.0 ± 1.4 ‰) between organic and conventional samples, respectively. Chemometric analyses of nitrate isotopes and extract chemistry revealed that the δ18 O of nitrate along with δ15 N and Ca2+ fully differentiated organic from conventional strawberry production. CONCLUSIONS: Our results show the Ti(III) reduction method provides a new low-cost and rapid analytical method to facilitate compound-specific δ15 N and δ18 O isotope analyses of nitrate in selected fruit types, and likely other food products, for the purposes of assessing nitrate fertilization practices of organic versus conventional production claims and to support authenticity investigations.

Food Matrix Reference Materials for Hydrogen, Carbon, Nitrogen, Oxygen, and Sulfur Stable Isotope-Ratio Measurements: Collagens, Flours, Honeys, and Vegetable Oils.

An international project developed, quality-tested, and measured isotope-delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope-delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins. An errors-in-variables regression model included the uncertainty associated with the measured and assigned values of the RMs, and it was applied centrally to normalize results and obtain consensus values and measurement uncertainties. Utilization of these new RMs should facilitate mutual compatibility of stable isotope data if accepted normalization procedures are applied and documented.