[Study on the Enhancement Intensity of Cd in Rice with Microwave-Assisted Laser-Induced Breakdown Spectroscopy].

As food safety problem has become the focus of attention all over the world, green detection methods of the contaminants in food is in accordance with the sustainable development of environment. Heavy metal pollutant Cd element in rice was used as the object of study in this work, laser induced breakdown spectroscopy (LIBS) and microwave assisted laser induced breakdown spectroscopy (MA-LIBS) were utilized to detect the blank and laboratory polluted rice samples respectively. The characteristic line of Cd Ⅰ 228.802 nm was employed as analytical line to discuss the enhancement effect of plasmas emission intensity for the analytical line of target element. Meanwhile, the actual concentration of Cd in rice was measured by anodic stripping voltammetry. The result displayed that LIBS can just detect the plasmas signals of the sample which contained 13.69 µg·g-1 cadmium for the laboratory polluted rice samples which concentration range from 2.16 to 13.69 µg·g-1, however, in the same experimental conditions, MA-LIBS can detect the plasmas signals of Cd in all of the contaminated rice samples successfully, and compared with LIBS, the plasmas emission intensity of Cd element was enhanced from 9 to 27 times. The results showed that the plasmas emission intensity of Cd element in rice can be enhanced effectively by MA-LIBS, and the detection sensitivity can be effectively improved.

[Influence of Spectral Pre-Processing on PLS Quantitative Model of Detecting Cu in Navel Orange by LIBS].

Cu in navel orange was detected rapidly by laser-induced breakdown spectroscopy (LIBS) combined with partial least squares (PLS) for quantitative analysis, then the effect on the detection accuracy of the model with different spectral data ptetreatment methods was explored. Spectral data for the 52 Gannan navel orange samples were pretreated by different data smoothing, mean centralized and standard normal variable transform. Then 319~338 nm wavelength section containing characteristic spectral lines of Cu was selected to build PLS models, the main evaluation indexes of models such as regression coefficient (r), root mean square error of cross validation (RMSECV) and the root mean square error of prediction (RMSEP) were compared and analyzed. Three indicators of PLS model after 13 points smoothing and processing of the mean center were found reaching 0. 992 8, 3. 43 and 3. 4 respectively, the average relative error of prediction model is only 5. 55%, and in one word, the quality of calibration and prediction of this model are the best results. The results show that selecting the appropriate data pre-processing method, the prediction accuracy of PLS quantitative model of fruits and vegetables detected by LIBS can be improved effectively, providing a new method for fast and accurate detection of fruits and vegetables by LIBS.

[Determination of Cu in Shell of Preserved Egg by LIBS Coupled with PLS].

In this work, the content of copper in the shell of preserved eggs were determined directly by Laser induced breakdown spectroscopy (LIBS), and the characteristics lines of Cu was obtained. The samples of eggshell were pretreated by acid wet digestion, and the real content of Cu was obtained by atomic absorption spectrophotometer (AAS). Due to the test precision and accuracy of LIBS was influenced by a serious of factors, for example, the complex matrix effect of sample, the enviro nment noise, the system noise of the instrument, the stability of laser energy and so on. And the conventional unvariate linear calibration curve between LIBS intensity and content of element of sample, such as by use of Schiebe G-Lomakin equation, can not meet the requirement of quantitative analysis. In account of that, a kind of multivariate calibration method is needed. In this work, the data of LIBS spectra were processed by partial least squares (PLS), the precision and accuracy of PLS model were compared by different smoothing treatment and five pretreatment methods. The result showed that the correlation coefficient and the accuracy of the PLS model were improved, and the root mean square error and the average relative error were reduced effectively by 11 point smoothing with Multiplicative scatter correction (MSC) pretreatment. The results of the study show that, heavy metal Cu in preserved egg shells can be direct detected accurately by laser induced breakdown spectroscopy, and the next step batch tests will been conducted to find out the relationship of heavy metal Cu content in the preserved egg between the eggshell, egg white and egg yolk. And the goal of the contents of heavy metals in the egg white, egg yolk can be knew through determinate the eggshell by the LIBS can be achieved, to provide new method for rapid non-destructive testing technology for quality and satety of agricultural products.