Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Overcoming barriers to sustainability by combining conceptual,visual, and networking systems

Sustainability challenges rarely align with the conventional boundaries of our disciplines, institutions and means of communication. To address these challenges amid real-world complexity, we need to think holistically and collaborate across disciplines. In this paper, we synthesise three themes: (1) more integrated conceptual frameworks; (2) digital visual communication which provides fluid expression of complex ideas and perceptions; and (3) online networks which can empower sustainability initiatives and communicate them across social and institutional barriers at a global scale. Each of these tools can help to overcome persistent barriers to sustainability. When used together, they provide a strategic basis for the design of digital collaboration platforms for addressing sustainability challenges. Using design thinking, we developed a Synergy Map which identifies relationships among a number of barriers to sustainability and conceptual and digital tools which help to address them. The Map identifies the potential for synthesising these tools into effective digital artefacts. We provide several examples and identify characteristics of particular value for overcoming barriers to sustainability. Combining new theoretical developments in sustainability sciences with recent advances in communication and networking technologies offers substantial potential for advancing sustainability on multiple fronts.     

Understanding the Causes of Spills From the Supply and Handling of Chemicals at Resource Construction Sites: A Case Study

An intermediate bulk container (IBC) was punctured during its handling, releasing a refined oil product onto land at a large construction site in an environmentally sensitive region of Australia. Understanding and controlling the risks from fuel, oil, and chemical spills on the current project was of critical importance as part of the project's overall approval, and ongoing compliance depended on the project committing to minimizing all chemical and petroleum hydrocarbon spills on the site. The telehandler (forklift) did not pierce the plastic of the IBC directly (as was expected to be the case) but rather one of the tynes caught on the underside of the metal base plate (pallet belly plate), despite numerous controls being in place at the time of spill (to limit the risks of damaging the IBC), revealing a previously unreported mechanism for a fluid spill from handling of petroleum hydrocarbons and related chemicals. The investigation team used a root cause analysis (RCA) technique, based on the fishbone (Ishikawa) diagram, which was undertaken with 12 expert contributors (from the project) to identify the underlying cause: The inspection process was inadequate. This study is a companion to the article published in Winter 2014 in Remediation (Guerin, 2014) covering multiple causes of spills from plant and equipment commonly used on construction and remediation projects. ©2015 Wiley Periodicals, Inc.     

Overestimation of self-reported driving exposure: Results from the SHRP2 Naturalistic Driving Study

Objectives: The accuracy of self-reported driving exposure has questioned the validity of using self-reported mileage to inform research questions. Studies examining the accuracy of self-reported driving exposure compared to objective measures find low validity, with drivers overestimating and underestimating driving distance. The aims of the current study were to (1) examine the discrepancy between self-reported annual mileage and driving exposure the following year and (2) investigate whether these differences depended on age and annual mileage.

Methods: Two estimates of drivers’ self-reported annual mileage collected during vehicle installation (obtained via prestudy questionnaires) and approximated annual mileage driven (based upon Global Positioning System data) were acquired from 3,323 participants who participated in the Strategic Highway Research Program 2 (SHRP2) Naturalistic Driving Study.

Results: A Wilcoxon signed rank test showed that there was a significant difference between self-reported and annual driving exposure during participation in SHRP 2, with the majority of self-reported responses overestimating annual mileage the following year, irrespective of whether an ordinal or ratio variable was examined. Over 15% of participants provided self-reported responses with over 100% deviation, which were exclusive to participants underestimating annual mileage. Further, deviations in reporting differed between participants who had low, medium, and high exposure, as well as between participants in different age groups.

Conclusions: These findings indicate that although self-reported annual mileage is heavily relied on for research, such estimates of driving distance may be an overestimate of current or future mileage and can influence the validity of prior research that has utilized estimates of driving exposure.     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.