Fractionation of stable carbon isotopes during acetate consumption by methanogenic and sulfidogenic microbial communities in rice paddy soils and lake sediments

Acetate is an important intermediate during the degradation of organic matter in anoxic flooded soils and sediments. Acetate is disproportionated to CH4 and CO2 by methanogenic or is oxidized to CO2 by sulfate-reducing microorganisms. These reactions result in carbon isotope fractionation, depending on the microbial species and their particular carbon metabolism. To learn more about the magnitude of the isotopic enrichment factors (ε) involved, acetate conversion to CH4 and CO2 was measured in anoxic paddy soils from Vercelli (Italy) and the International Rice Research Institute (IRRI, the Philippines) and in anoxic lake sediments from the northeastern and the southwestern basins of Lake Fuchskuhle (Germany). Acetate consumption was measured using samples of paddy soil or lake sediment suspended in water or in phosphate buffer (pH 7.0), both in the absence and presence of sulfate (gypsum), and of methyl fluoride (CH3F), an inhibitor of aceticlastic methanogenesis. Under methanogenic conditions, values of εac for acetate consumption were always in a range of −21 ‰ to −17 ‰ but higher in the lake sediment from the southwestern basin (−11 ‰). Under sulfidogenic conditions εac values tended to be slightly lower (−26 ‰ to −19 ‰), especially when aceticlastic methanogenesis was inhibited. Again, εac in the lake sediment of the southwestern basin was higher (−18 ‰ to −14 ‰). Determination of εCH4 from the accumulation of 13C in CH4 resulted in much lower values (−37 ‰ to −27 ‰) than from the depletion of 13C in acetate (−21 ‰ to −17 ‰ ), especially when acetate degradation was measured in buffer suspensions. The microbial communities were characterized by sequencing the bacterial 16S rRNA (ribosomal ribonucleic acid) genes as well as the methanogenic mcrA and sulfidogenic dsrB genes. The microbial communities were quite different between lake sediments and paddy soils but were similar in the sediments of the two lake basins and in the soils from Vercelli and the IRRI, and they were similar after preincubation without and with addition of sulfate (gypsum). The different microbial compositions could hardly serve for the prediction of the magnitude of enrichment factors.

Analysis of Multiresidue Pesticides in Agricultural Paddy Soils Near Industrial Areas in Korea by GC–MS/MS and LC–MS/MS Using QuEChERS Extraction with dSPE Clean-Up

Pesticides have been used to control pests in agricultural fields and storage systems before circulating agricultural products to markets. A tandem mass spectrometry, equipped with gas chromatographic separation (GC–MS/MS) or ultra-performance liquid chromatographic separation (LC–MS/MS), was used to monitor residual pesticides in Korean rice paddy soils. Selective multiple reaction monitoring was employed during the analyses to achieve multiresidue pesticide analysis using GC–MS/MS and LC–MS/MS of 342 pesticides. In this study, QuEChERS extraction was employed with a dSPE clean-up to establish an effective pretreatment process. The limit of detection (LOD) and limit of quantification (LOQ) were set up for all pesticides, and method validation was performed for linearity and recovery at levels of 10 and 50 mg kg−1 in the untreated soil sample. All pesticides satisfied the acceptable recovery range of 70–120%, within less than 20% RSD values, except for ametoctradin and gibberellic acid. In the paddy soil analyses, tricyclazole was the most frequently detectable pesticide, followed by oxadiazon, endosulfan, and chlorantraniliprole. Continuous monitoring of residual pesticides in paddy soils should be conducted due to the translocation of some systemic pesticides from soils to crop plants, and the impact of residual pesticides on the environment.

Spatial content and variability of mercury in agricultural soils in the province of Valencia (Spain), with an emphasis on those dedicated to rice crop

<p>Mercury (Hg) is a metal potentially dangerous that can accumulate in soils, move to plants and cause significant ecotoxicological risks. The province of Valencia is the third in Spain and has a great agricultural, industrial and tourist vocation; it has an area of 10,763 km<sup>2</sup>, of which it devotes 272,978 ha to cultivation, most of which are irrigated soils. To the south of the city of Valencia, is the Albufera Natural Park (ZEPA area and Ramsar wetland) with 14,806 ha dedicated to rice cultivation. Pollution and burning of rice straw in rice paddies are serious problems. Therefore, the concentration of Hg in agricultural soils in the province of Valencia according to use, with an emphasis on rice paddy soils, and spatial distribution were determined; and the effects of rice straw burning on Hg accumulation on rice paddy soils was assessed. Systematic sampling was carried out throughout the agricultural area at an intensity of a grid of 8 x 8 km, in which samples composed of soil between 0 and 20 cm were collected in a total of 98 plots; and a simple random sampling in the case of rice paddies in 35 sites, distinguishing between plots where the incineration of rice straw was carried out and where it was not. The concentration of Hg was determined with a direct DMA-80 Milestone analyzer in the previously pulverized sample. The detection limit was 1.0 g kg<sup>-1</sup>, the recovery was 95.1% to 101.0% ± 4.0%. The analyses were performed in triplicate. A basic descriptive statistic (means, medians, deviations, and ANOVA) was performed. Samples were grouped according to land use. For geostatistic analysis and in order to obtain the map of the spatial distribution of the concentration of Hg in soils, the classical geostatistic technique was used by ordinary kriging. The concentration of Hg in the soils of the province of Valencia showed great variability. The soils of the rice paddies together with those dedicated to the cultivation of citrus and horticultural of the coastal plain, showed the highest levels of Hg, in contrast to the soils of the interior areas dedicated to dry crops (vineyards, olive, almond and fodder). Spatial analysis reflected a concentration gradient from west to east, suggesting that the Hg in the soils of the interior has a geochemical origin, while in the coast soils it is of anthropic origin. On the other hand, it was observed that the burning of rice straw increased the Hg concentration in rice paddy soils. This research is the first information on the distribution of Hg in the soils of the province of Valencia and a contribution that can help weigh the effects of open burning of rice straw on Valencian rice paddies.</p>