Impact of Simulated California Rice-Growing Conditions on Chlorantraniliprole Partitioning

Chlorantraniliprole (3-bromo-<i>N</i>-[4-chloro-2-methyl-6-(methylcarbamoyl)­phenyl]-1-(3-chloro-2-pyridine-2-yl)-1<i>H</i>-pyrazole-5-carboxamide, CAP; water solubility 1.023 mg·L^–1) was recently registered for application on California rice fields. Air– and soil–water partitioning of CAP were investigated under simulated California rice field conditions through calculation of <i>K</i>_H and Δ_aw<i>H</i> and a batch equilibrium method following OECD 106 guidelines, respectively. <i>K</i>_H and Δ_aw<i>H</i> were determined to be 1.69 × 10^–16 – 2.81 × 10^–15 atm·m³·mol^–1 (15–35 °C) and 103.68 kJ·mol^–1, respectively. Log­(<i>K</i>_oc) ranged from 2.59 to 2.96 across all soil and temperature treatments. Log­(<i>K</i>_<i>F</i>) ranged from 0.61 to 1.14 across all soil, temperature, and salinity treatments. Temperature and salinity increased sorption significantly at 35 °C (<i>P</i> < 0.05) and 0.2 M (<i>P</i> < 0.0001), respectively, while soil properties impacted sorption across all treatments. Overall results, corroborated using the Pesticides in Flooded Applications Model, indicate that volatilization of CAP is not a major route of dissipation and sorption of CAP to California rice field soils is moderately weak and reversible

Reactive Oxygen Species and Chromophoric Dissolved Organic Matter Drive the Aquatic Photochemical Pathways and Photoproducts of 6PPD-quinone under Simulated High-Latitude Conditions

The photochemical degradation pathways of 6PPD-quinone (6PPDQ, 6PPD-Q), a toxic transformation product of the tire antiozonant 6PPD, were determined under simulated sunlight conditions typical of high-latitude surface waters. Direct photochemical degradation resulted in 6PPDQ half-lives ranging from 17.5 h at 20 °C to no observable degradation over 48 h at 4 °C. Sensitization of excited triplet-state pathways using Cs+ and Ar purging demonstrated that 6PPDQ does not decompose significantly from a triplet state relative to a singlet state. However, assessment of processes involving reactive oxygen species (ROS) quenchers and sensitizers indicated that singlet oxygen and hydroxyl radical do significantly contribute to the degradation of 6PPDQ. Investigation of these processes in natural lake waters indicated no difference in attenuation rates for direct photochemical processes at 20 °C. This suggests that direct photochemical degradation will dominate in warm waters, while indirect photochemical pathways will dominate in cold waters, involving ROS mediated by chromophoric dissolved organic matter (CDOM). Overall, the aquatic photodegradation rate of 6PPDQ will be strongly influenced by the compounding effects of environmental factors such as light screening and temperature on both direct and indirect photochemical processes. Transformation products were identified via UHPLC-Orbitrap mass spectrometry, revealing four major processes: (1) oxidation and cleavage of the quinone ring in the presence of ROS, (2) dealkylation, (3) rearrangement, and (4) deamination. These data indicate that 6PPDQ can photodegrade in cool, sunlit waters under the appropriate conditions: t1/2 = 17.4 h tono observable decrease (direct); t1/2 = 5.2-11.2 h (indirect, CDOM)

A light touch: solar photocatalysis detoxifies oil sands process-affected waters prior to significant treatment of naphthenic acids or acid extractable organics

The toxicity of oil sands process-affected water (OSPW) has been associated to its dissolved organics, a complex mixture of naphthenic acid fraction components (NAFCs). Here, we evaluated solar treatment with buoyant photocatalysts (BPCs) as a candidate passive advanced oxidation process (P-AOP) for OSPW remediation, according to both analytical chemistry and standard rainbow trout (Oncorhynchus mykiss) and fathead minnow (Pimephales promelas) whole effluent toxicity (WET) bioassays. Solar photocatalysis with BPCs fully degraded naphthenic acids (NAs) and acid extractable organics (AEO) in 3 different OSPW samples, however fish toxicity was eliminated well before concentrations of dissolved organics had significantly diminished, within <2 days of sunlight exposure for all OSPWs. Classical NAs and AEO, traditionally considered among the principal toxicants in OSPW, were not correlated with OSPW toxicity herein. Instead, petroleomic mass spectrometry (MS) analysis revealed low polarity organosulfur NAFCs – O2S− and OS+ (putatively naphthenic sulfoxides), together composing <10% of the total AEO – were correlated with WET outcomes, and apparently accounted for the majority of waters’ toxicity, as described by a physiologically-based model (PBM) of tissue partitioning. These results demonstrate that complete elimination of OSPW toxicity per standard WET bioassays is achievable without significant changes to overall concentrations of dissolved organics, suggesting that most AEO are toxicologically benign, and toxicity may instead be driven by only a small subset of NAFCs, which are preferentially photocatalytically treated. These findings have implications for OSPW release, for which a less extensive but more selective treatment may be required than previously expected

Novel Lesions of Bones and Joints Associated with Chikungunya Virus Infection in Two Mouse Models of Disease: New Insights into Disease Pathogenesis

Chikungunya virus is an arbovirus spread predominantly by Aedes aegypti and Ae. albopictus mosquitoes, and causes debilitating arthralgia and arthritis. While these are common manifestations during acute infection and it has been suggested they can recur in patients chronically, gaps in knowledge regarding the pathogenesis still exist. Two established mouse models were utilized (adult IRF 3/7 -/- -/- and wild-type C57BL/6J mice) to evaluate disease manifestations in bones and joints at various timepoints. Novel lesions in C57BL/6J mice consisted of periostitis (91%) and foci of cartilage of necrosis (50% of mice at 21 DPI). Additionally, at 21 DPI, 50% and 75% of mice exhibited periosteal bone proliferation affecting the metatarsal bones, apparent via histology and μCT, respectively. μCT analysis did not reveal any alterations in trabecular bone volume measurements in C57BL/6J mice. Novel lesions demonstrated in IRF 3/7 -/- -/- mice at 5 DPI included focal regions of cartilage necrosis (20%), periosteal necrosis (66%), and multifocal ischemic bone marrow necrosis (100%). Contralateral feet in 100% of mice of both strains had similar, though milder lesions. Additionally, comparison of control IRF 3/7 -/- -/- and wild-type C57BL/6J mice demonstrated differences in cortical bone. These experiments demonstrate novel manifestations of disease similar to those occurring in humans, adding insight into disease pathogenesis, and representing new potential targets for therapeutic interventions. Additionally, results demonstrate the utility of μCT in studies of bone and joint pathology and illustrate differences in bone dynamics between mouse strains

Absolute and Relative Vaccine Effectiveness of Primary and Booster Series of COVID-19 Vaccines (mRNA and Adenovirus Vector) Against COVID-19 Hospitalizations in the United States, December 2021–April 2022

BackgroundCoronavirus disease 2019 (COVID-19) vaccine effectiveness (VE) studies are increasingly reporting relative VE (rVE) comparing a primary series plus booster doses with a primary series only. Interpretation of rVE differs from traditional studies measuring absolute VE (aVE) of a vaccine regimen against an unvaccinated referent group. We estimated aVE and rVE against COVID-19 hospitalization in primary-series plus first-booster recipients of COVID-19 vaccines.MethodsBooster-eligible immunocompetent adults hospitalized at 21 medical centers in the United States during December 25, 2021-April 4, 2022 were included. In a test-negative design, logistic regression with case status as the outcome and completion of primary vaccine series or primary series plus 1 booster dose as the predictors, adjusted for potential confounders, were used to estimate aVE and rVE.ResultsA total of 2060 patients were analyzed, including 1104 COVID-19 cases and 956 controls. Relative VE against COVID-19 hospitalization in boosted mRNA vaccine recipients versus primary series only was 66% (95% confidence interval [CI], 55%-74%); aVE was 81% (95% CI, 75%-86%) for boosted versus 46% (95% CI, 30%-58%) for primary. For boosted Janssen vaccine recipients versus primary series, rVE was 49% (95% CI, -9% to 76%); aVE was 62% (95% CI, 33%-79%) for boosted versus 36% (95% CI, -4% to 60%) for primary.ConclusionsVaccine booster doses increased protection against COVID-19 hospitalization compared with a primary series. Comparing rVE measures across studies can lead to flawed interpretations of the added value of a new vaccination regimen, whereas difference in aVE, when available, may be a more useful metric

Vaccine effectiveness of primary series and booster doses against covid-19 associated hospital admissions in the United States: living test negative design study

AbstractObjectiveTo compare the effectiveness of a primary covid-19 vaccine series plus booster doses with a primary series alone for the prevention of hospital admission with omicron related covid-19 in the United States.DesignMulticenter observational case-control study with a test negative design.SettingHospitals in 18 US states.Participants4760 adults admitted to one of 21 hospitals with acute respiratory symptoms between 26 December 2021 and 30 June 2022, a period when the omicron variant was dominant. Participants included 2385 (50.1%) patients with laboratory confirmed covid-19 (cases) and 2375 (49.9%) patients who tested negative for SARS-CoV-2 (controls).Main outcome measuresThe main outcome was vaccine effectiveness against hospital admission with covid-19 for a primary series plus booster doses and a primary series alone by comparing the odds of being vaccinated with each of these regimens versus being unvaccinated among cases versus controls. Vaccine effectiveness analyses were stratified by immunosuppression status (immunocompetent, immunocompromised). The primary analysis evaluated all covid-19 vaccine types combined, and secondary analyses evaluated specific vaccine products.ResultsOverall, median age of participants was 64 years (interquartile range 52-75 years), 994 (20.8%) were immunocompromised, 85 (1.8%) were vaccinated with a primary series plus two boosters, 1367 (28.7%) with a primary series plus one booster, and 1875 (39.3%) with a primary series alone, and 1433 (30.1%) were unvaccinated. Among immunocompetent participants, vaccine effectiveness for prevention of hospital admission with omicron related covid-19 for a primary series plus two boosters was 63% (95% confidence interval 37% to 78%), a primary series plus one booster was 65% (58% to 71%), and for a primary series alone was 37% (25% to 47%) (P<0.001 for the pooled boosted regimens compared with a primary series alone). Vaccine effectiveness was higher for a boosted regimen than for a primary series alone for both mRNA vaccines (BNT162b2 (Pfizer-BioNTech): 73% (44% to 87%) for primary series plus two boosters, 64% (55% to 72%) for primary series plus one booster, and 36% (21% to 48%) for primary series alone (P<0.001); mRNA-1273 (Moderna): 68% (17% to 88%) for primary series plus two boosters, 65% (55% to 73%) for primary series plus one booster, and 41% (25% to 54%) for primary series alone (P=0.001)). Among immunocompromised patients, vaccine effectiveness for a primary series plus one booster was 69% (31% to 86%) and for a primary series alone was 49% (30% to 63%) (P=0.04).ConclusionDuring the first six months of 2022 in the US, booster doses of a covid-19 vaccine provided additional benefit beyond a primary vaccine series alone for preventing hospital admissions with omicron related covid-19.Readers’ noteThis article is a living test negative design study that will be updated to reflect emerging evidence. Updates may occur for up to two years from the date of original publication