In the field of chemical warfare agents (CWAs), ethanolamines are important building blocks for the preparation of nerve agents belonging to the V-series such as VX and VR as well as the nitrogen-based mustards. In this work, the determination of three members in this class of Schedule 2B reportable chemicals, namely N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA), and N,N-diisopropylethanolamine (DIEA) by electron ionization gas chromatography-mass spectrometry (EI-GC-MS) is presented. The three dialkylethanolamines were spiked in a high organic content soil matrix featured during the 45th Organization for the Prohibition of Chemical Weapons (OPCW) proficiency test (PT) at two separate concentrations each (1 and 10 mu g/g separately), simulating values often encountered during these tests. The N,N-dialkylethanolamines were O-alkylated using benzyl bromide and sodium carbonate at 55 degree celsius and were detected as their benzylated versions by electron ionization GC-MS. The benzylation of each dialkylethanolamine yielded derivatives with higher molecular weight and therefore different GC-MS profiles such as longer retention times and sharper peak chromatography relative to their unmodified counterparts. These characteristics enable the analytical chemist to detect and confirm these important CWA-related chemicals specifically in instances where they are present in low concentrations (i.e. <10 mu g/g) among more abundant interferences.

Heavy-duty trucks are a major source of transportation-related greenhouse gas and criteria pollutant emissions. One approach to reducing the climate and health impacts of these trucks is to transition them to zero-emission technologies such as battery electric trucks (BETs). To date, BETs have been deployed mostly in drayage application. As the performance of BETs has improved in recent years, there is increasing interest in using BETs also in regional haul application. This paper examines real-world activity patterns of 15 heavy-duty BETs in regional haul application using data collected from early deployments of these trucks across eight different fleets in Southern California. The results show that the BETs are typically used on routes (or tours) that are much shorter than their driving ranges. They often make one or two tours per day, and are usually charged at the end of each tour. Due to the variation in the time of day that the BETs are operated, they are charged at different times of day, spreading the charging load throughout the day. In addition, the results indicate that, on average, about half of the BET's operations occur in or around disadvantaged communities, providing emission reduction benefits to these communities.

Despite their prohibition by the Chemical Weapons Convention, nerve agents (NAs) remain in use against military and civilian targets. Due to their high reactivity, NAs readily degrade to phosphonic acids, making them important markers in the inspection of areas of presumed NA use. In this work, we assess the use of benzylation to modify ethyl- and pinacolyl methylphosphonic acids, degradation products of VX and Soman respectively, for their efficient detection in a soil matrix at similar to 10 and similar to 1 mu g/g using GC-MS. The soil matrix, Sandy Loam (SL), was chosen for its ubiquitous nature, complex composition with silica particles embedded in clay, and low organic content. In this study, we demonstrate that benzylation via benzyl bromide yields a LOD = 25.6 ng/mL for benzylated-EMPA and LOD = 30.1 ng/mL for benzylated-PMPA. This is superior to the use of p-methoxybenzyl trichloroacetimidate in providing stable phosphonic acid ester derivatives for analysis. A base-modified procedure for p-methoxybenzylation was explored in this study yielding a LOD = 29.1 ng/mL for p-methox- ybenzylated-EMPA and LOD = 39.8 ng/mL forp-methoxybenzylated-PMPA. Both benzylation pathways (benzyl bromide and p-methoxybenzyl trichloroacetimidate) can be used to yield phosphonic acid derivatives that provide further confirmation of these Soman and VX degradation products in soil samples in investigative scenarios. The work herein represents the first application of benzylation methods for the analysis of these NA markers in the acidic, silicon-based SL soil.

Even though heavy-duty battery electric trucks (BETs) have become commercially available, their range limitation still hinders widespread adoption. Drayage has been regarded as a suitable application for early BETs due to typically having limited daily mileage. However, drayage operation can vary widely and some form of range extension may still be needed for BETs operating in this application. In this paper, wireless charging at port terminals is proposed for this purpose. Potential wireless charging zones at port terminals are identified, and efficacy of wireless charging to extend BET range in drayage operation is verified by simulating the activity of 20 BETs from a drayage operator serving the ports of Los Angeles and Long Beach, using a microscopic BET energy consumption model. Furthermore, an optimization problem is formulated for optimal wireless charging zone planning from the port authority's perspective, considering subsets of the identified zones, and charging power options to choose from, for different budget ranges. In this context, zone planning means determining which areas of the port terminals should be selected for installing wireless charging systems, and what level of charging power should be for each selected zone's system. For each budget range, the optimization problem is solved using genetic algorithm to determine an optimal zone plan that provides the maximum amount of energy through wireless charging per unit cost of installation. The results show that wireless charging can aid improving activity completion of the simulated fleet by 5%, and further optimizing the zone plan can achieve similar performance with lower cost.

Pinacolyl alcohol (PA), a key forensic marker for the nerve agent Soman (GD), is a particularly difficult analyte to detect by various analytical methods. In this work, we have explored the reaction between PA and 1,1 '-carbonyldiimidazole (CDI) to yield pinacolyl 1H-imidazole-1-carboxylate (PIC), a product that can be conveniently detected by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS). Regarding its GC-MS profile, this new carbamate derivative of PA possesses favorable chromatographic features such as a sharp peak and a longer retention time (RT = 16.62 min) relative to PA (broad peak and short retention time, RT = 4.1 min). The derivative can also be detected by LC-HRMS, providing an avenue for the analysis of this chemical using this technique where PA is virtually undetectable unless present in large concentrations. From a forensic science standpoint, detection of this low molecular weight alcohol signals the past or latent presence of the nerve agent Soman (GD) in a given matrix (i.e., environmental or biological). The efficiency of the protocol was tested separately in the analysis and detection of PA by EI-GC-MS and LC-HRMS when present at a 10 mu g/mL in a soil matrix featured in the 44th PT and in a glycerol-rich liquid matrix featured in the 48th Official Organization for the Prohibition of Chemical Weapons (OPCW) Proficiency Test when present at a 5 mu g/mL concentration. In both scenarios, PA was successfully transformed into PIC, establishing the protocol as an additional tool for the analysis of this unnatural and unique nerve agent marker by GC-MS and LC-HRMS.

An extraction protocol from silt sediment of fentanyl and three analogs: acetylfentanyl, thiofentanyl and acetylthiofentanyl, spiked at two concentrations each and separately (at similar to 1 and similar to 10 mu g/g), is described. In addition, the identity of the fentanyls preliminarily identified by electron ionization gas chromatography-mass spectrometry (EI-GC-MS) analysis, can be corroborated by reacting each opioid in the silt's extract with 2,2,2-trichloroethoxycarbonyl chloride (Troc-Cl). Reaction between Troc-Cl and each opioid generates two unique products that can be used to retrospectively identify the original opioid therefore serving as a corroborating tool for known opioids as well as new, unknown fentanyl analogs.

Connected vehicle (CV) technology has the potential to greatly improve the safety, mobility, and environmental sustainability of traffic. Many CV applications require the vehicle position as input, which is primarily provided by global navigation satellite systems (GNSS). Although a large number of those applications (e.g., Intersection Movement Assist) require vehicle positioning to have lane-level accuracy, it has been shown that the type of positioning system typically used by CVs currently cannot provide consistent lane-level accuracy, even under open-sky conditions. In order to address this gap, we have evaluated an enhanced positioning system that adds little, if any, to the cost of the CV. It consists of a single-frequency real-time kinematic (RTK)-capable GNSS receiver onboard the vehicle, which utilizes Radio Technical Commission for Maritime Services (RTCM) differential corrections transmitted over dedicated short-range communications (DSRC) by the roadside infrastructure. Tests on a moving vehicle show that this system could provide lane-level accuracy over 95% of the time in open-sky conditions. These tests also show the DSRC to be an effective means of disseminating RTCM corrections, given the intersection spacings and communication ranges in the test. However, neither RTCM nor the more commonly used space-based augmentation system (SBAS) differential corrections appeared to improve the positioning accuracy of GNSS in urban canyons.

The benzylation of three low molecular weight N,N-disubstituted ethanolamines related to chemical warfare agents (CWAs) to furnish derivatives with improved gas chromatography-mass spectrometry (GC-MS) profiles is described. Due to their low molecular weight and polar nature, N,N-disubstituted ethanolamines are notoriously difficult to detect by routine GC-MS analyses during Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency tests (PTs), particularly in scenarios when they are present at low levels (similar to 1-10 ppm) amidst more abundant interferences. Our studies revealed that the optimal derivatization conditions involved the treatment of the ethanolamine with benzyl bromide in the presence of an inorganic base (e. g., Na2CO3) in dichloromethane at 55 degrees C for 2 h. This optimized set of conditions was then successfully applied to the derivatization of N,N-dimethylethanolamine, N,N-diethylethanolamine and N,N-diisopropylethanolamine present separately at 1 and 10 mu g/mL concentrations in a glycerol-rich matrix sample featured in the 48th OPCW PT. The benzylated derivatives of the three ethanolamines possessed retention times long enough to clear the massive glycerol-containing matrix interferences. The protocol herein is introduced as an alternative method for derivatization of these CWA and pharmaceutically important species and should find broad applicability in laboratories where routine forensic analysis is carried out.

Detection of illicit drugs in the environment, particularly in soils, often suggests the present or past location of a clandestine production center for these substances. Thus, development of efficient methods for the analysis and detection of these chemicals is of paramount importance in the field of chemical forensics. In this work, a method involving the extraction and retrospective confirmation of fentanyl, acetylfentanyl, thiofentanyl, and acetylthiofentanyl using trichloroethoxycarbonylation chemistry in a high clay‐content soil is presented. The soil was spiked separately with each fentanyl at two concentrations (1 and 10 μg/g) and their extraction accomplished using ethyl acetate and aqueous NH4OH (pH ~ 11.4) with extraction recoveries ranging from ~56% to 82% for the high‐concentration (10 μg/g) samples while ranging from ~68% to 83% for the low‐concentration (1 μg/g) samples. After their extraction, residues containing each fentanyl were reacted with 2,2,2‐trichloroethoxycarbonyl chloride (Troc‐Cl) to generate two unique and predictable products from each opioid that can be used to retrospectively confirm their presence and identity using EI‐GC‐MS. The method's limit of detection (MDL/LOD) for Troc‐norfentanyl and Troc‐noracetylfentanyl were estimated to be 29.4 and 31.8 ng/mL in the organic extracts. In addition, the method's limit of quantitation for Troc‐norfentanyl and Troc‐noracetylfentanyl were determined to be 88.2 and 95.5 ng/mL, respectively. Collectively, the results presented herein strengthen the use of chloroformate chemistry as an additional chemical tool to confirm the presence of these highly toxic and lethal substances in the environment.

Class-8 battery electric trucks (BET) are modeled and simulated in this paper to determine their capability in fulfilling real-world drayage activity under different operational scenarios. Potential wireless charging zones at port terminals are identified, and wireless charging opportunities are introduced to improve drayage activity fulfillment of BETs. The results show that current BETs would be able to fulfill approximately 79-86% of the real-world drayage activity sample used in this research, and that the ability to receive wireless opportunity charging at port terminals could help increase the activity fulfillment to about 84-91%.

Rationale Detection of 3-quinuclidinol (3Q), a marker for the chemical warfare agent 3-quinuclidinyl benzilate, is very difficult by gas chromatography-mass spectrometry (GC/MS), providing low, broad signals even when analyzed in isolated form. Therefore, a method that can convert 3Q into a substrate with enhanced detectability by GC/MS would be an important tool for its analysis. Methods 2,2,2-Trichloroethoxycarbonyl chloride (TrocCl) was used in the derivatization of 3Q in three different soils of varying composition and total organic content (Virginia type A soil, Nebraska EPA standard soil and Ottawa sand) when present at a 10 mu g g(-1) concentration in each. A direct derivatization protocol and one involving the pre-extraction of the analyte were evaluated for their individual efficiencies and subsequent analysis using electron ionization GC/MS. Results The practical derivatization of 3Q, when present at low levels (10 mu g g(-1)) in three different soil matrices, was found to be rapid (1 h) and to take place smoothly at ambient temperature (and as low as 4 degrees C). The method detection limit was determined to be 30 ng mL(-1) for the Virginia type A soil, 49 ng mL(-1) for the Nebraska EPA standard soil and 72 ng mL(-1) for the Ottawa sand sample. Conclusions An expedient and practical derivatization method for 3Q, a chemical warfare degradation product difficult to detect by GC/MS, has been realized using trichloroethyl chloroformate. The reaction provides 3Q-Troc, a derivative with better detectability than 3Q by electron ionization GC/MS such as peak sharpness and a unique mass spectrum for its unambiguous identification.

Surface transportation accounts for a large fraction of greenhouse gas emissions around the world. Vehicles powered by internal combustion engines are becoming increasingly fuel efficient and produce less emissions through a number of technological improvements. One technology category is providing real-time “eco-driving” feedback to drivers, so that they drive more efficiently. Since hard accelerations have a major effect on vehicle fuel consumption and emissions, some eco-driving systems have been developed to provide drivers with feedback through the accelerator pedal in order to mitigate these events. This study evaluates one such system called the Reactive Force Pedal (RFP) that provides different degrees of force feedback to the driver. This study examined two levels of force feedback (LOW and HIGH) that were applied to 40 drivers while driving on a prescribed route in Southern California. Detailed driving data (speed, acceleration, fuel consumption, etc.) were collected for baseline, LOW RFP, and HIGH RFP settings, and subsequently compared. The data were also used to compare different emission models in order to gain insight on future scenario estimation methods. The results show that there is 2% - 3% improvement in fuel economy with the LOW setting, and approximately 3% - 5% improvement with the HIGH setting, when consider positive acceleration events. The technology has different effects among different drivers.

In recent years, the development of connected and automated vehicle (CAV) technology has inspired numerous advanced applications targeted at improving existing transportation systems. As one of the widely studied applications of CAV technology, connected eco-driving takes advantage of Signal Phase and Timing (SPaT) information from traffic signals to enable CAVs to approach and depart from signalized intersections in an energy-efficient manner. However, the majority of the connected eco-driving studies have been numerical or microscopic traffic simulations. Only few studies have implemented the application on real vehicles, and even fewer have been focused on heavy-duty trucks. In this study, we developed a connected eco-driving system and equipped it on a heavy-duty diesel truck using cellular-based wireless communications. Field trials were conducted in the City of Carson, California, along two corridors with six connected signalized intersections capable of communicating their SPaT information. Early results showed the benefits of the system in smoothing the speed profiles of the equipped truck when approaching the connected signalized intersections.

A practical and efficient protocol for the derivatization and detection by GC-EI-MS of isopropyl-, pinacolyl- and cyclohexylmethylphosphonic acids, key diagnostic degradation products of the nerve agents sarin, soman and cyclosarin respectively, in six different types of soil matrices is presented. The method involves the in situ conversion of the phosphonic acids to their respective methyl esters using trimethyloxonium tetrafluoroborate when present in the soils at low levels (10 mu g g(-1)) without any prior extractions or soil preparation. The soils employed in our study were Nebraska EPA soil, Georgia soil, silt, Virginia type A soil, regular sand and Ottawa sand and were chosen for their vast differences in composition and physical features. Appealing attributes of the protocol include its rapidity (t < 30 min), mildness (ambient temperature), and practicality that includes the production of the phosphonic methyl esters that can be easily detected by GC-EI-MS and corroborated with the instrument's internal NIST spectral library or the Organisation for the Prohibition of Chemical Weapons (OPCW) central analytical database (OCAD v. 21_2019). The overall efficacy of the protocol was then tested on a soil sample featured in the 44th OPCW PT that our laboratory participated in. After preparing the soil so as to give pinacolyl methylphosphonic acid at a 5 mu g g(-1) concentration, the acid was successfully methylated and detected by GC-EI-MS. The protocol's performance mirrors that of the universally employed diazomethane protocol but accomplishes this without any of the explosive hazards and time consuming reagent preparation commonly associated with it. Published by Elsevier B.V.

A multivariate model was developed to attribute samples to a synthetic method used in the production of sulfur mustard (HD). Eleven synthetic methods were used to produce 66 samples for model construction. Three chemists working in both participating laboratories took part in the production, with the aim to introduce variability while reducing the influence of laboratory or chemist specific impurities in multivariate analysis. A gas chromatographic/mass spectrometric data set of peak areas for 103 compounds was subjected to orthogonal partial least squares - discriminant analysis to extract chemical attribution signature profiles and to construct multivariate models for classification of samples. For one- and two-step routes, model quality allowed the classification of an external test set (16/16 samples) according to synthesis conditions in the reaction yielding sulfur mustard. Classification of samples according to first-step methodology was considerably more difficult, given the high purity and uniform quality of the intermediate thiodiglycol produced in the study. Model performance in classification of aged samples was also investigated.

Chemical attribution signatures (CAS) associated with different synthetic routes used for the production of Russian VX (VR) were identified. The goal of the study was to retrospectively determine the production method employed for an unknown VR sample. Six different production methods were evaluated, carefully chosen to include established synthetic routes used in the past for large scale production of the agent, routes involving general phosphorus-sulfur chemistry pathways leading to the agent, and routes whose main characteristic is their innate simplicity in execution. Two laboratories worked in parallel and synthesized a total of 37 batches of VR via the six synthetic routes following predefined synthesis protocols. The chemical composition of impurities and byproducts in each route was analyzed by GC/MS-EI and 49 potential CAS were recognized as important markers in distinguishing these routes using Principal Component Analysis (PCA). The 49 potential CAS included expected species based on knowledge of reaction conditions and pathways but also several novel compounds that were fully identified and characterized by a combined analysis that included MS-CI, MS-EI and HR-MS. The CAS profiles of the calibration set were then analyzed using partial least squares discriminant analysis (PLS-DA) and a cross validated model was constructed. The model allowed the correct classification of an external test set without any misclassifications, demonstrating the utility of this methodology for attributing VR samples to a particular production method. This work is part one of a three-part series in this Forensic VSI issue of a Sweden United States collaborative effort towards the understanding of the CAS of VR in diverse batches and matrices. This part focuses on the CAS in synthesized batches of crude VR and in the following two parts of the series the influence of food matrices on the CAS profiles are investigated.

On-road heavy-duty diesel vehicles are a major contributor of oxides of nitrogen (NOx) emissions. In the US, many heavy-duty diesel vehicles employ selective catalytic reduction (SCR) technology to meet the 2010 emission standard for NOx. Typically, SCR needs to be at least 200°C before a significant level of NOx reduction is achieved. However, this SCR temperature requirement may not be met under some real-world operating conditions, such as during cold starts, long idling, or low speed/low engine load driving activities. The frequency of vehicle operation with low SCR temperature varies partly by the vehicle's vocational use. In this study, detailed vehicle and engine activity data were collected from 90 heavy-duty vehicles involved in a range of vocations, including line haul, drayage, construction, agricultural, food distribution, beverage distribution, refuse, public work, and utility repair. The data were used to create real-world SCR temperature and engine load profiles and identify the fraction of vehicle operating time that SCR may not be as effective for NOx control. It is found that the vehicles participated in this study operate with SCR temperature lower than 200°C for 11-70% of the time depending on their vocation type. This implies that real-world NOx control efficiency could deviate from the control efficiency observed during engine certification.