UAS Chromatograph for Atmospheric Trace Species (UCATS) – a versatile instrument for trace gas measurements on airborne platforms

UCATS (the UAS Chromatograph for Atmospheric Trace Species) was designed and built for observations of important atmospheric trace gases from unmanned aircraft systems (UAS) in the upper troposphere and lower stratosphere (UTLS). Initially it measured major chlorofluorocarbons (CFCs) and the stratospheric transport tracers nitrous oxide (N2O) and sulfur hexafluoride (SF6), using gas chromatography with electron capture detection. Compact commercial absorption spectrometers for ozone (O3) and water vapor (H2O) were added to enhance its capabilities on platforms with relatively small payloads. UCATS has since been reconfigured to measure methane (CH4), carbon monoxide (CO), and molecular hydrogen (H2) instead of CFCs and has undergone numerous upgrades to its subsystems. It has served as part of large payloads on stratospheric UAS missions to probe the tropical tropopause region and transport of air into the stratosphere; in piloted aircraft studies of greenhouse gases, transport, and chemistry in the troposphere; and in 2021 is scheduled to return to the study of stratospheric ozone and halogen compounds, one of its original goals. Each deployment brought different challenges, which were largely met or resolved. The design, capabilities, modifications, and some results from UCATS are shown and described here, including changes for future missions.

Determination of Pesticides Residue by GC-ECD in Vegetables from Cameron Highlands, Malaysia and Their Human Health Risk Assessment

Gas chromatography-electron capture detection (GC-ECD) method has been developed to determine the residues of pyrethroid (PYRs), organophosphorus (OPPs) and organochlorine (OCPs) pesticide in 97 leafy vegetable samples collected from Cameron Highlands, Malaysia. The mean residual concentration of PYRs, OPPs and OCPs ranged from 0.04–17, 0.03–44.4 and 0.03–100 μg kg–1 respectively. The sum of pesticides concentration increased in the order mustard < spinach < celery < cauliflower < lettuce < broccoli < cabbage. The results revealed that levels of maximum residue limit (MRL) for OCPs were violated by lettuce (7.7%), for OPPs, it exceeded mostly in cabbage (24.8%) and for PYRs only one cabbage sample exceeded the MRL. Health risk estimation revealed that hazard quotients (HQs) for OCPs, OPPs and PYRs were <1.0, showing less risk to consumers. However, the hazard indices (HIs) for OPPs were >1.0 for children (1.4) and for adults (0.4) which signify the potential health risk to consumers.

Experimental justification of the maximum possible concentration (MPC) of dichlorohexafluorobutene in a working area

To date, there have been no exposure standards for air concentrations of 1,4-dichlorohexafluorobutene (DCHF) in the work areas. The study was aimed to assess the toxicity of DCHF and to evaluate health hazard in acute, subacute, and chronic experiments. It was found that the substance was highly hazardous, DL50 in mice after intragastric injection was 79.0 mg/kg, СL50 was 229.0 mg/m3, and in rats these values were 86,0 mg/kg and 670,0 mg/m3. In animals, DCHF had a moderate local irritative effect on animal skin and ocular mucous membranes, as well as the skin resorptive effect. The 18.2 mg/m3 threshold limit concentration for a single inhalation exposure to DCHF was defined based on the changes in behavior responses and blood parameters. The 30-day subacute inhalation experiment revealed the pronounced cumulative effect of the substance. The 4-months chronic inhalation study showed that the exposure of experimental rats to 16.8 mg/m3 concentration of DCHF resulted in impaired function of central nervous system and cardiac activity, altered hematologic, biochemical, acid-base, and blood gas values, as well as in morphological alterations in lungs, which persisted after the 30-day recovery period. The chronic exposure threshold defined for DCHF was 2.2 mg/m3, and the defined no observable effect level was 0.24 mg/m3. Based on the study results, the maximum permissible concentration of DCHF in the air of the working area of 0.2 mg/m3 was confirmed and approved, the substance was assigned hazard class 2, vapor + aerosol + (specific protection of skin and eyes required). Gas chromatographic method using electron-capture detection for determination of DCHF mass air concentration in the work areas has been developed and approved.

A comparison of sodium sulfite, ammonium chloride, and ascorbic acid for quenching chlorine prior to disinfection byproduct analysis

This study compared 3 commonly used quenching agents for dechlorinating samples prior to disinfection byproduct (DBP) analysis under typical drinking water sampling conditions for a representative suite of chlorination byproducts. Ascorbic acid and sodium sulfite quenched the residual free chlorine to below detection within 5 seconds. Ammonium chloride did not quench the chlorine to below detection with up to a 70% molar excess, which agrees with published ammonium chloride-chlorine chemistry. With respect to the DBPs, ascorbic acid worked well for the trihalomethanes and haloacetic acids, except for dibromoiodomethane, which exhibited 2.6–28% error when using ascorbic acid compared to non-quenched control samples. Sodium sulfite also worked well for the trihalomethanes (and performed similarly to ascorbic acid for dibromoiodomethane) and was the best performing quenching agent for MX and the inorganic DBPs, but contributed to the decay of several emerging DBPs, including several halonitromethanes and haloacetamides. Ammonium chloride led to considerable errors for many DBPs, including 27–31% errors in chloroform concentrations after 24 hours of storage. This work shows that ascorbic acid is suitable for many of the organic DBPs analyzed by gas chromatography-electron capture detection and that sodium sulfite may be used for simultaneous chlorite, chlorate, and bromate analysis.

UAS Chromatograph for Atmospheric Trace Species (UCATS) – a versatile instrument for trace gas measurements on airborne platforms

UCATS (the UAS Chromatograph for Atmospheric Trace Species) was designed and built for observations of important atmospheric trace gases from unmanned aircraft systems (UAS) in the upper troposphere and lower stratosphere (UT/LS). Initially it measured major chlorofluorocarbons (CFCs) and the stratospheric transport tracers nitrous oxide (N2O) and sulfur hexafluoride (SF6), using gas chromatography with electron capture detection. Compact ozone (O3) and water vapor (H2O) instruments were added to enhance science missions on platforms with relatively small payloads. Over the past decade, UCATS has been reconfigured to measure methane (CH4), carbon monoxide (CO), and molecular hydrogen (H2) instead of CFCs and has undergone numerous upgrades to its subsystems. It has served as part of large payloads on stratospheric UAS missions to probe the tropical tropopause region and transport of air into the stratosphere, in piloted aircraft studies of greenhouse gases, transport, and chemistry in the troposphere, and will soon return to the study of stratospheric ozone depletion, one of the original goals for UCATS. Each deployment brought different challenges, which were largely met or resolved. The design, capabilities, modifications and some results from UCATS are shown and described here, including changes for upcoming missions.

Strategies for SERS Detection of Organochlorine Pesticides

Organochlorine pesticides (OCPs) embody highly lipophilic hazardous chemicals that are being phased out globally. Due to their persistent nature, they are still contaminating the environment, being classified as persistent organic pollutants (POPs). They bioaccumulate through bioconcentration and biomagnification, leading to elevated concentrations at higher trophic levels. Studies show that human long-term exposure to OCPs is correlated with a large panel of common chronic diseases. Due to toxicity concerns, most OCPs are listed as persistent organic pollutants (POPs). Conventionally, separation techniques such as gas chromatography are used to analyze OCPs (e.g., gas chromatography coupled with mass spectrometry (GC/MS)) or electron capture detection (GC/ECD). These are accurate, but expensive and time-consuming methods, which can only be performed in centralized lab environments after extensive pretreatment of the collected samples. Thus, researchers are continuously fueling the need to pursue new faster and less expensive alternatives for their detection and quantification that can be used in the field, possibly in miniaturized lab-on-a-chip systems. In this context, surface enhanced Raman spectroscopy (SERS) represents an exceptional analytical tool for the trace detection of pollutants, offering molecular fingerprint-type data and high sensitivity. For maximum signal amplification, two conditions are imposed: an efficient substrate and a high affinity toward the analyte. Unfortunately, due to the highly hydrophobic nature of these pollutants (OCPs,) they usually have a low affinity toward SERS substrates, increasing the challenge in their SERS detection. In order to overcome this limitation and take advantage of on-site Raman analysis of pollutants, researchers are devising ingenious strategies that are synthetically discussed in this review paper. Aiming to maximize the weak Raman signal of organochlorine pesticides, current practices of increasing the substrate’s performance, along with efforts in improving the selectivity by SERS substrate functionalization meant to adsorb the OCPs in close proximity (via covalent, electrostatic or hydrophobic bonds), are both discussed. Moreover, the prospects of multiplex analysis are also approached. Finally, other perspectives for capturing such hydrophobic molecules (MIPs—molecularly imprinted polymers, immunoassays) and SERS coupled techniques (microfluidics—SERS, electrochemistry—SERS) to overcome some of the restraints are presented.