RESUMO
By assessing the changes in stable isotope compositions within individual pesticide molecules, Compound Specific Isotope Analysis (CSIA) holds the potential to identify and differentiate sources and quantify pesticide degradation in the environment. However, the environmental application of pesticide CSIA is limited by the general lack of knowledge regarding the initial isotopic composition of active substances in commercially available formulations used by farmers. To address this limitation, we established a database aimed at cataloguing and disseminating isotopic signatures in commercial formulations to expand the use of pesticide CSIA. Our study involved the collection of 25 analytical standards and 120 commercial pesticide formulations from 23 manufacturers. Subsequently, 59 commercial formulations and 25 standards were extracted, and each of their active substance was analyzed for both δ13C (n = 84) and δ15N CSIA (n = 43). The extraction of pesticides did not cause significant isotope fractionation (Δ13C and Δ15N < 1). Incorporating existing literature data, stable carbon and nitrogen isotope signatures varied in a relatively narrow range among pesticide formulations for different pesticides (Δ13C and Δ15N < 10) and within different formulations for a single substance (Δ13C and Δ15N < 2). Overall, this suggests that pesticide CSIA is more suited for identifying pesticide transformation processes rather than differentiating pesticide sources. Moreover, an inter-laboratory comparison showed similar δ13C (Δ13C ≤ 1.2 ) for the targeted substances albeit varying GC-IRMS instruments. Insignificant carbon isotopic fractionation (Δ13C < 0.5) was observed after 4 years of storing the same pesticide formulations, confirming their viability for long-term storage at 4 °C and future inter-laboratory comparison exercises. Altogether, the ISOTOPEST database, in open access for public use and additional contributions, marks a significant advancement in establishing an environmentally relevant pesticide CSIA approach.
Assuntos
Praguicidas , Praguicidas/análise , Isótopos de Carbono/análise , Isótopos de Nitrogênio/análise , Fracionamento QuímicoRESUMO
Multi-element compound-specific stable isotope analysis (ME-CSIA) allows monitoring the environmental behavior and transformation of most common and persistent contaminants. Recent advancements in analytical techniques have extended the applicability of ME-CSIA to organic micropollutants, including pesticides. Nevertheless, the application of this methodology remains unexplored concerning harmful insecticides such as methoxychlor, a polar organochlorine pesticide usually detected in soil and groundwater. This study introduces methods for dual carbon and chlorine compound-specific stable isotope analysis (δ13C-CSIA and δ37Cl-CSIA) of both methoxychlor and its metabolite, methoxychlor olefin, with a sensitivity down to 10 and 100 mg/L, and a precision lower than 0.3 and 0.5 for carbon and chlorine CSIA, respectively. Additionally, three extraction and preconcentration techniques suitable for ME-CSIA of the target pesticides at environmentally relevant concentrations were also developed. Solid-phase extraction (SPE) and liquid-solid extraction (LSE) effectively extracted methoxychlor (107 ± 27 % and 87 ± 13 %, respectively) and its metabolite (91 ± 27 % and 106 ± 14 %, respectively) from water and aquifer slurry samples, respectively, with high accuracy (Δδ13C and Δδ37Cl ≤ ± 1 ). Combining CSIA with polar organic chemical integrative samplers (POCISs) for the extraction of methoxychlor and methoxychlor olefin from water samples resulted in insignificant fractionation for POCIS-CSIA (Δδ13C ≤ ± 1 ). A relevant sorption of methoxychlor was detected within the polyethersulfones membranes of the POCISs resulting in temporary carbon isotope fractionation depending on the sorbed mass fraction during the first deployment days. This highlights the critical role of the interactions of polar analytes with POCIS sorbents and membranes in the performance of this method. Altogether, this study proposes a proof of concept for ME-CSIA of methoxychlor and its metabolites, opening the door for future investigations of their sources and transformation processes in contaminated sites.