Gibaek Kim

Detection of Nutrient Elements and Contamination by Pesticides in Spinach and Rice Samples Using Laser-Induced Breakdown Spectroscopy (LIBS)

The laser-induced breakdown spectroscopy (LIBS) technique was applied to quantify nutrients (Mg, Ca, Na, and K) in spinach and rice and to discriminate pesticide-contaminated products in a rapid manner. Standard reference materials (spinach leaves and unpolished rice flour) were used to establish a relationship between LIBS intensity and the concentration of each element (Mg, Ca, Na, and K) (i.e., calibration line). The limits of detection (LODs) for Mg, Ca, Na, and K were found to be 29.63, 102.65, 36.36, and 44.46 mg/kg in spinach and 7.54, 1.76, 4.19, and 6.70 mg/kg in unpolished rice, respectively. Concentrations of those nutrient elements present in spinach and unpolished rice from a local market were determined by using the calibration lines and compared with those measured with ICP-OES, showing good agreement. The data also suggested that the LIBS technique with the chemometric method (PLS-DA) could be a great tool to distinguish pesticide-contaminated samples from pesticide-free samples in a rapid manner even though they have similar elemental compositions. Misclassification rates were found to be 0 and 2% for clean spinach and pesticide-contaminated spinach, respectively, by applying the PLS-DA model established from the training set of data to predict the classes of test samples.

Rapid detection of soils contaminated with heavy metals and oils by laser induced breakdown spectroscopy (LIBS)

A laser induced breakdown spectroscopy (LIBS) coupled with the chemometric method was applied to rapidly discriminate between soils contaminated with heavy metals or oils and clean soils. The effects of the water contents and grain sizes of soil samples on LIBS emissions were also investigated. The LIBS emission lines decreased by 59-75% when the water content increased from 1.2% to 7.8%, and soil samples with a grain size of 75 μm displayed higher LIBS emission lines with lower relative standard deviations than those with a 2mm grain size. The water content was found to have a more pronounced effect on the LIBS emission lines than the grain size. Pelletizing and sieving were conducted for all samples collected from abandoned mining areas and military camp to have similar water contents and grain sizes before being analyzed by the LIBS with the chemometric analysis. The data show that three types of soil samples were clearly discerned by using the first three principal components from the spectral data of soil samples. A blind test was conducted with a 100% correction rate for soil samples contaminated with heavy metals and oil residues.

Determination of Heavy Metal Distribution in PM10 During Asian Dust and Local Pollution Events Using Laser Induced Breakdown Spectroscopy (LIBS)

Hourly concentrations of heavy metals in PM10 samples were continuously measured using Laser Induced Breakdown Spectroscopy (LIBS) to determine the metal distribution among Asian Dust (AD) events, local pollution events, and nonevents. Quantification of metals was performed by establishing a calibration line between 24 h average data determined by the ICP-MS after filter sampling and LIBS intensity data. It was found that in AD and local pollution events, significant anthropogenic heavy metals, such as Pb, Cr, Ni, and Zn, were detected compared to a nonevent, and that crustal elements (e.g., Al, Ca, Mg) were more abundant in the AD events than those in a local pollution event or nonevent. The AD events were further classified into “nonpolluted AD” and “polluted AD” events, depending on the air mass transport pathways. During “polluted AD” events where the air mass passed over industrialized zones, both crustal (Al, Ca, Mg) and anthropogenic (Cr, Ni, Zn) metal elements simultaneously increased with time, suggesting that the AD particles could not only include crustal elements but also have a significant quantity of anthropogenic heavy metals. The concentration of anthropogenic heavy metals (Cr + Pb + Zn) was the highest in the AD3 event in order of AD3 (polluted) > AD1 (polluted) > local pollution > AD2 (nonpolluted). However, the PM10-weighted value (Cr + Pb + Zn/PM10) was the highest in the local pollution event where concentrations of only anthropogenic heavy metals increased. Also, the hourly LIBS data was successfully used to discriminate metal contributions between AD events and local pollution events or among AD events by employing a chemometric method. Copyright 2012 American Association for Aerosol Research

Kriging interpolation method for laser induced breakdown spectroscopy (LIBS) analysis of Zn in various soils

Laser induced breakdown spectroscopy (LIBS) was used to determine Zn concentrations in various types of soils, and discarding and kriging interpolation methods were combined to enhance the accuracy and precision of the LIBS analysis. In order to determine Zn concentrations in 10 field soils, the discarding method was used for pre-treatment of LIBS data acquisition. A remarkable decrease of relative standard deviation was observed indicating a significant increase of pulse-to-pulse precision. Nine artificial soil sets containing different contents of sand, kaolin, and goethite were manufactured for the interpolation database, and they displayed differing LIBS broadband spectra due to their respective sample matrices. In addition, the calibration slope of each soil set varied significantly showing up to a 3.36-fold difference. We found that the matrix effect derived from sand, kaolin, and goethite contents can be determined by detecting major elements in soil (Si, Al, and Fe) from LIBS analysis without additional measurements. The kriging interpolation model was applied using the database obtained from the artificial soil sets. The concentration of Zn in field soils calculated from data treatment methods showed significantly accurate results when compared to ICP-OES analysis results. By minimizing factors affecting the LIBS result, heavy metal concentrations in various types of soils can be determined using a developed database without calibration.

Mixing state of size-selected submicrometer particles in the Arctic in May and September 2012.

Aerosols have been associated with large uncertainties in estimates of the radiation budget and cloud formation processes in the Arctic. This paper reports the results of a study of in situ measurements of hygroscopicity, fraction of volatile species, mixing state, and off-line morphological and elemental analysis of Aitken and accumulation mode particles in the Arctic (Ny-Ålesund, Svalbard) in May and September 2012. The accumulation mode particles were more abundant in May than in September. This difference was due to more air mass flow from lower latitude continental areas, weaker vertical mixing, and less wet scavenging in May than in September, which may have led to a higher amount of long-range transport aerosols entering the Arctic in the spring. The Aitken mode particles observed intermittently in May were produced by nucleation, absent significant external mixing, whereas the accumulation mode particles displayed significant external mixing. The occurrence of an external mixing state was observed more often in May than in September and more often in accumulation mode particles than in Aitken mode particles, and it was associated more with continental air masses (Siberian) than with other air masses. The external mixing of the accumulation mode particles in May may have been caused by multiple sources (i.e., long-range transport aerosols with aging and marine aerosols). These groups of externally mixed particles were subdivided into different mixing structures (internal mixtures of predominantly sulfates and volatile organics without nonvolatile species and internal mixtures of sulfates and nonvolatile components, such as sea salts, minerals, and soot). The variations in the mixing states and chemical species of the Arctic aerosols in terms of their sizes, air masses, and seasons suggest that the continuous size-dependent measurements observed in this study are useful for obtaining better estimates of the effects of these aerosols on climate change.

Comparison of Hygroscopicity, Volatility, and Mixing State of Submicrometer Particles between Cruises over the Arctic Ocean and the Pacific Ocean.

Ship-borne measurements of ambient aerosols were conducted during an 11 937 km cruise over the Arctic Ocean (cruise 1) and the Pacific Ocean (cruise 2). A frequent nucleation event was observed during cruise 1 under marine influence, and the abundant organic matter resulting from the strong biological activity in the ocean could contribute to the formation of new particles and their growth to a detectable size. Concentrations of particle mass and black carbon increased with increasing continental influence from polluted areas. During cruise 1, multiple peaks of hygroscopic growth factor (HGF) of 1.1-1.2, 1.4, and 1.6 were found, and higher amounts of volatile organic species existed in the particles compared to that during cruise 2, which is consistent with the greater availability of volatile organic species caused by the strong oceanic biological activity (cruise 1). Internal mixtures of volatile and nonhygroscopic organic species, nonvolatile and less-hygroscopic organic species, and nonvolatile and hygroscopic nss-sulfate with varying fractions can be assumed to constitute the submicrometer particles. On the basis of elemental composition and morphology, the submicrometer particles were classified into C-rich mixture, S-rich mixture, C/S-rich mixture, Na-rich mixture, C/P-rich mixture, and mineral-rich mixture. Consistently, the fraction of biological particles (i.e., P-containing particles) increased when the ship traveled along a strongly biologically active area.

Characteristics of tire wear particles generated by a tire simulator under various driving conditions

Physicochemical properties of pure tire wear particles (TWPs) were investigated in a laboratory. A tire simulator installed in an enclosing chamber was employed to eliminate artifacts caused by interfering particles during the generation and measurement of TWPs. TWP particulate matter (PM2.5 and PM10) was correlated with tire speed ( r > 0.94) and load ( r > 0.99). Their mass size distributions showed that TWP mode diameters ranged between 3 and 4 μm (unimodal). Tire wear caused by slip events resulted in an increase in the number concentration (ca. 8.4 × 105 cm-3) of particles (mainly ultrafine particles (UFPs)) at low PM2.5 and PM10 values (1 and 2 μg m-3, respectively). During braking events, UFPs were emitted at an early stage, with an increase in number concentration (up to 1.1 × 107 cm-3); a high mass concentration (3.6 mg m-3) was observed at a later stage via the coagulation of early emitted UFPs and condensation. On the basis of morphology and elemental composition, TWPs generally had elongated (micrometer-scale) and round/irregular (submicrometer-scale) shapes and they were classified into C/Si-rich, heavy metal-containing, S-containing, and mineral-containing particles. This study determined that TWP emissions can vary with changes in driving condition.

Development of laser-induced breakdown spectroscopy (LIBS) with timed ablation to improve detection efficiency

ABSTRACT A laser-induced breakdown spectrometer (LIBS) was developed for determining the elemental composition of individual airborne particles. The system employs two lasers focused on a narrow beam of particles. A continuous wave laser placed upstream scatters light from particles, while a pulse laser downstream ablates the particles. The scattered light from the upstream laser is used to trigger the downstream pulse laser, resulting in more accurate hitting of the particles than a free-firing laser system without the triggering signal (i.e., constant pulse laser firing). Various laboratory-generated aerosols (NaCl, MgCl2, KCl, and CaCl2) were used to evaluate the newly developed LIBS system. Particles were tightly focused into a center line with a sheath air focusing system using an optimum aerosol-to-sheath air velocity ratio. The locations of both the scattering laser and pulse laser beams were precisely controlled by a motorized X-Y stage controller. Data showed that for the LIBS with the triggering system, the hitting efficiency (%) of particles (200–600 nm) significantly increased (e.g., 350 nm particles had more than 26 times higher hitting efficiency at 1,000 particles/cm3), and much lower limits of particle size (∼200 nm) and number concentration (<100 particles/cm3) were achieved compared to the free-firing laser condition. Additionally, the hitting rate (hits/min) significantly increased with the triggering system. Our results suggest that the LIBS with the triggering system can be useful for real-time detection of elements of particles existing at low number concentrations (e.g., atmospheric particles) and for the determination of the variation of elemental composition among particles.

Ultra short X-ray source based on the nonlinear Thomson scattering of femtosecond lasers from plasma-accelerated electron beams

In this paper, we propose an experimental scheme for a compact X-ray source which can produce X-ray pulses with 10 femtosecond duration. This novel X-ray source is based on the nonlinear Thomson backscattering of terawatt ultrashort infra-red laser from MeV plasma accelerated electrons, which are now routinely generated from the laser-wakefield accelerators. The synchronization between the TW laser and e-beam can simply be achieved via a jitter-less optical delay. At KERI, a 2 TW 700 fs laser system has been installed and the experiment on e-beam generation is ongoing. Here we show some simulation results for the typical ultrashort e-beam generation from the LWFA and the basic calculations for the X-ray generation.

Self-injected laser wakefield acceleration in tapered plasma densities

Extremely strong electric fields generated by relativistic plasma waves can be used to accelerate electrons to high energy. This can be done either by external injection or self-injection of plasma electrons. In this paper, we report that plasma electrons by the self-injected laser wakefield acceleration using a sharp density transition can gain significantly higher energies when the trapped particles are accelerated in a tapered plasma density. Two-dimensional (2-D) simulation studies show that significantly higher energies can be obtained with an increasing plasma density although space-charge effect of the trapped electrons deforms and deteriorates the laser wakefield severely.