Application of laser-induced breakdown spectroscopy for detection of elements in flowback water samples from shale gas wells.

Laser-induced breakdown spectroscopy (LIBS) was applied to rapidly detect elements in flowback water samples from shale gas wells in Oklahoma. Two types of LIBS systems (aerosolization and collection on a substrate) were used. The LIBS with an aerosolization system provided rapid determination of elements in flowback water, but moisture present in the chamber and variation in the water droplet size could make quantification difficult. In the substrate collection system, a comparison among substrate types showed that a hydrophilic cellulose filter gave the most homogeneous sample distribution after drying and provided the best performance. The elements in flowback water samples were also determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES). ICP-OES data showed spatial variations for the elements among the different wells. Among the elements, K showed the highest variation (relative standard ${\rm deviation} = {62.8}\% $deviation=62.8%) and Mg the lowest (relative standard ${\rm deviation} = {39.1}\% $deviation=39.1%). Good correlations (${ r} = {0.98 - 0.99}$r=0.98-0.99) were observed between Ca, K, Mg, and Na LIBS peak areas determined using the cellulose filter and their mass concentrations (ppm) measured by ICP-OES for aqueous solutions. The limits of detection for Ca, K, Mg, and Na by LIBS were 122 ppm, 68 ppm, 36 ppm, and 142 ppm, respectively. Both the LIBS and ICP-OES data showed that element concentrations in the flowback water samples were in the order of Na, Ca, Mg, and K from highest to lowest. Our data suggest that the LIBS technique could rapidly detect elements in flowback water samples on site. However, accurate quantification of elements present in low concentrations in water samples is limited.

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.

Application of laser-induced breakdown spectroscopy for real-time detection of contamination particles during the manufacturing process.

A stand-off laser-induced breakdown spectroscopy (LIBS) system was developed to determine the elemental composition of contamination particles during semiconductor manufacturing. It successfully detected laboratory-generated monodisperse (size=200 nm and 300 nm) CaCl2 particles and internally mixed particles of CaCl2, MgCl2, NaCl, and KCl. Temperature and pressure effects on the LIBS emission signals were investigated. The peak area and signal-to-noise ratio of the emission lines increased with the temperature (25°C-250°C). Stronger emission lines were observed at higher pressure. Although temperature and pressure affect the LIBS signals, the developed stand-off LIBS could be employed for real-time detection of the elemental composition of contamination particles.

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.

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.

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.

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.