Application of copper(II)-based chemicals induces CH3Br and CH3Cl emissions from soil and seawater

Methyl bromide (CH3Br) and methyl chloride (CH3Cl) are major carriers of atmospheric bromine and chlorine, respectively, which can catalyze stratospheric ozone depletion. However, in our current understanding, there are missing sources associated with these two species. Here we investigate the effect of copper(II) on CH3Br and CH3Cl production from soil, seawater and model organic compounds: catechol (benzene-1,2-diol) and guaiacol (2-methoxyphenol). We show that copper sulfate (CuSO4) enhances CH3Br and CH3Cl production from soil and seawater, and it may be further amplified in conjunction with hydrogen peroxide (H2O2) or solar radiation. This represents an abiotic production pathway of CH3Br and CH3Cl perturbed by anthropogenic application of copper(II)-based chemicals. Hence, we suggest that the widespread application of copper(II) pesticides in agriculture and the discharge of anthropogenic copper(II) to the oceans may account for part of the missing sources of CH3Br and CH3Cl, and thereby contribute to stratospheric halogen load.

Efficacy and Phytotoxicity Assessment of Successive Application of Methyl Bromide and Cold Treatment on Export Strawberry Fruits

Recently, spotted wing Drosophila, Drosophila suzukii, is globally prevalent and causes agricultural losses to many fruits. To export Korean strawberry, methyl bromide fumigation is required to remove D. suzukii infestations, but Korean strawberry farmers are worried about fruit damage because methyl bromide can cause phytotoxicity on fresh commodities. In this report, we assessed the efficacy and phytotoxicity of single and successive application of methyl bromide and cold treatment on an export variety of strawberry to reduce fruit damage. The currently recommended dosage of methyl bromide, 40 g/m3 for 3 h at 18 °C, was enough to control all stages of D. suzukii without phytotoxicity. A dosage of 20 g/m3 of methyl bromide treatment for 3 h, followed by 1 d of cold (0 °C) treatment, showed 100% mortality in all growth stages of D. suzukii without fruit damage. Successive application of methyl bromide and cold treatment shows potential as a method of decreasing phytotoxicity and reducing the use of methyl bromide for environmental considerations.

Ethyl Formate as a Methyl Bromide Alternative for Fumigation of Citrus: Efficacy, Fruit Quality, and Workplace Safety

Ethyl formate (EF) was evaluated as a potential alternative to methyl bromide (MB) for phytosanitary treatment of imported citrus fruit in the Republic of Korea. Planococcus citri (Risso) (Hemiptera: Pseudococcidae), a mealybug with known tolerance against EF and MB, was used as a representative pest to test efficacy of the two fumigants against eggs. In nine commercial-scale refrigerated container (67.5 m3) trials using imported orange, lemon and grapefruit, EF applied at the currently approved dose for citrus (70 g·m-3 at 5°C for 4 h, developed for Aspidiotus excisus Green (Hemiptera: Diaspididae), a species less EF tolerant than P. citri) resulted in 76.9–98.3% mortality of P. citri eggs. The EF treatment did not affect the sugar content or the color of peel and pulp of the treated fruit. When oranges were treated according to the current MB (64 g·m-3 at >5°C for 2 h) or EF treatment guidelines, the concentration of fumigant around the fruit fluctuated between 9.4 and 185.1 ppm for EF and 9.5–203.0 ppm for MB during the 72-h post-fumigation processes (venting [0–2 h], transportation to storage [2–24 h], and storage periods [24–72 h]) with both EF and MB maintained between 10 and 100 ppm during the storage period. Considering the efficacy of EF, its apparent lack of phytotoxicity, and its more manageable threshold limit value for humans (100 ppm EF compared to 1 ppm MB for an 8-h time weighted average exposure), our results suggest that EF may be a promising alternative to MB for the phytosanitary treatment of imported citrus in Korea.

Top-down and bottom-up estimates of anthropogenic methyl bromide emissions from eastern China

Methyl bromide (CH3Br) is a potent ozone-depleting substance (ODS) that has both natural and anthropogenic sources. CH3Br has been used mainly for preplant soil fumigation, post-harvest grain and timber fumigation, and structural fumigation. Most non-quarantine/pre-shipment (non-QPS) uses have been phased-out in 2005 for non-Article 5 (developed) countries and in 2015 for Article 5 (developing) countries under the Montreal Protocol on Substances that Deplete the Ozone Layer; some uses have continued under critical use exemptions (CUEs). Under the Protocol, individual nations are required to report annual data on CH3Br production and consumption for quarantine/pre-shipment (QPS) uses, non-QPS uses and CUEs to the United Nations Environment Programme (UNEP). In this study, we analyzed high precision, in situ measurements of atmospheric concentrations of CH3Br obtained at the Gosan station on Jeju island, Korea, from 2008 to 2019. The background concentrations of CH3Br in the atmosphere at Gosan declined from 8.5 ± 0.8 ppt in 2008 to 7.4 ± 0.6 ppt in 2019 at a rate of −0.13 ± 0.02 ppt yr−1. At Gosan, we also observed periods of persistent concentrations (pollution events) elevated above the decreasing background in continental air masses from China. Statistical back trajectory analyses showed that these pollution events predominantly trace back to CH3Br emissions from eastern China. Using an inter-species correlation (ISC) method with the reference trace species CFC-11 (CCl3F), we estimate anthropogenic CH3Br emissions from eastern China at 4.1 ± 1.3 Gg yr−1 in 2008–2019, approximately 2.9 ± 1.3 Gg yr−1 higher than the bottom-up emission estimates reported to UNEP. Possible non-fumigation CH3Br sources – rapeseed production and biomass burning – were assessed and it was found that the discrepancy is more likely due to unreported or incorrectly reported QPS and non-QPS fumigation uses. These largely-unreported anthropogenic emissions of CH3Br are confined to eastern China and account for 30–40 % of anthropogenic global CH3Br emissions. They are likely due to delays in the introduction of CH3Br alternatives, such as sulfuryl fluoride (SO2F2), heat, irradiation and a possible lack of industry awareness of the need for regulation of CH3Br production and use.

Scaled-up ethyl formate fumigation to replace methyl bromide on traded mushroom to disinfest mushroom fly (Lycoriella mali)

Mushroom fly, Lycoriella mali (Diptera: Sciaridae), is the primary pest in imported mushrooms. The amount of Tricholoma matsutake imported from China increases every fall when it is harvested. When importing T. matsutake, disinfestation using methyl bromide (MB) or phosphine (PH3) is performed to prevent the introduction of L. mali. However, MB will be phased out due to ozone-depletion, chronic toxicity to workers, and residual issues. PH3 fumigation in mushroom disinfestation requires a long exposure time (24 h). In this study, we used ethyl formate (EF), which can replace MB and reduce exposure time. The efficacy of EF, PH3 and EF + PH3 on L. mali was evaluated. Using 4-h EF fumigation at 5 °C, the 3rd and 4th instar was the most tolerant stage in terms of 99% killed lethal concentration × time products (LCt99%). When 4-h EF fumigation at 5 °C was applied on all stages of L. mali, the LCt99% values of EF were 73.1 g h/m3 to the 1st and 2nd instar, 112.9 g h/m3 to the 3rd and 4th instar, 68.9 g h/m3 to pupae, and 20.1 g h/m3 to adult. It was confirmed that combination treatment with EF + PH3 had a synergistic effect on L. mali. The LCt99% of EF + 0.5 g/m3 of PH3 to the 3rd and 4th instar was 48.3 g h/m3. When only 140 g/m3 of EF was applied for 4 h at > 5 °C and 35 g/m3 of EF + 0.5 g/m3 of PH3 for 4 h at > 5 °C in commercial trials containing T. matsutake, proven efficacy (100%) on L. mali was confirmed. In the case of EF treatment only, phytotoxic damage occurred due to high Ct products, and there was no phytotoxic damage in combination treatment with EF + PH3. This study provides a new guideline for EF + PH3 combination treatment within a shorter exposure time (4 h) than existing PH3 treatment (24 h) and replacement of MB use.

Supplemental fumigant placement improves root-knot and Fusarium wilt management for tomatoes produced on a raised bed, plasti-culture system in Florida’s Myakka fine sand.

Fresh-market tomatoes are produced on a raised-bed, plasti-culture system that relies heavily on soil applied, pre-plant fumigants for the management of soil borne pathogens, nematodes and weeds. Since the transition from methyl bromide to alternative fumigants, growers have experienced a resurgence of several soil borne pests and pathogens, including root-knot nematode caused by Meloidogyne spp. and Fusarium wilt caused by Fusarium oxysporum f.sp. lycopersici Race 3 (FOL). This resurgence is attributed to the inability of the alternative fumigants to effectively disperse through the soil in the same manner as methyl bromide. Two supplemental fumigation strategies, the application of chloropicrin below bed edges (supplemental PIC) and broadcast, deep shank applications of 1,3-dichloropropene (deep shank 1,3-D), were evaluated in conjunction with standard raised-bed applications of Pic-Clor 60, Pic-Clor 80, and Pic 100 covered with either a virtually impermeable film (VIF) or totally impermeable film (TIF). Large plot replicated studies were conducted in two separate commercial tomato fields with a history of production losses caused by root-knot nematode and Fusarium wilt. Deep shank 1,3-D applications significantly reduced the recovery of root-knot and total parasitic nematodes across field sites prior to the preparation of raised beds. Both supplemental PIC and deep shank 1,3-D reduced root-knot galling and Fusarium wilt incidence; although, the latter supplemental treatment statistically had the greatest impact. Neither the fumigant applied within raised beds nor plastic film had a significant effect on root-knot galling or Fusarium wilt. Although both supplemental fumigation strategies had a significant effect on pest and disease pressure, neither statistically improved tomato yields based on small sub-plot harvests. Controlled lab experiments confirmed the fungicidal activity of 1,3-dichloropropene against FOL, with LD75, LD90, LD95, and LD99 corresponding to estimated field application rates of 56.1, 93.5, 121.6, 184.7 L/ha, respectively. Results demonstrate how fumigant placement can improve pest and disease control activity with current fumigant alternatives to methyl bromide; and further support the broader pesticidal activity of some chemical fumigants.