Determination of seventeen major and trace elements in new float glass standards for use in forensic comparisons using laser ablation inductively coupled plasma mass spectrometry.

Consensus concentration values for seventeen (17) major and trace elements typically present in soda-lime glass manufactured using the "float " process and used in the quantitative analysis and forensic comparison of glass samples were determined using laser ablation (LA) micro sampling coupled to inductively coupled plasma mass spectrometry (ICP-MS). This is the first reporting of the chemical characterization of a new set of float glass intended for use as matrix-matched calibration standards in the forensic analysis and comparison of glass by LA-ICP-MS using a standard test method (ASTM E2927-16e1). Three Corning Float Glass Standards (CFGS) were manufactured at low, medium, and high concentrations of 32 elements typically encountered in float glass samples as found in forensic casework. This work describes an international collaboration among seven (7) laboratories to evaluate the homogeneity of the three glass materials and reports the consensus concentrations values of 17 elements at three concentration levels. Eight (8) sets of independent results from LA-ICP-MS analysis using the standard test method of analysis and one set of micro-X-ray Fluorescence Spectrometry (µXRF) data (using method ASTM E2926-17) resulted in typically <3% relative standard deviation (RSD) within each lab and < 5% RSDs among all labs participating in the study for the concentration ranges using sampling spots between 50 µm - 100 µm in diameter. These results suggest that the new calibration standards are homogeneous for most elements at the small sampling volumes (~ 90 µm deep by ~80 µm in diameter) reported and show excellent agreement among the different participating labs. Consensus concentration values are determined using a previously reported calibration standard (FGS 2) and checked with a NIST 1831 SRM®. A collaboration with National Institute of Standards and Technology (NIST) scientists to certify these glasses as SRMs, including the certification of the quantitative analysis of the minor and trace element content, for future distribution by NIST is ongoing.

Quantitative MRI and laser ablation-inductively coupled plasma-mass spectrometry imaging of iron in the frontal cortex of healthy controls and Alzheimer's disease patients.

Accumulation of iron within the cortex of Alzheimer's disease (AD) patients has been reported by numerous MRI studies using iron-sensitive methods. Validation of iron-sensitive MRI is important for the interpretation of in vivo findings. In this study, the relation between the spatial iron distribution and T2∗-weighted MRI in the human brain was investigated using a direct comparison of spatial maps of iron as detected by T2∗-weighted MRI, iron histochemistry and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), in postmortem brain tissue of the medial frontal gyrus of three control subjects and six AD patients. In addition, iron levels measured by LA-ICP-MS and three quantitative MRI methods, namely R2∗ (=1/T2∗), image phase and quantitative susceptibility mapping (QSM), were compared between 19 AD and 11 controls. Histochemistry results we obtained with the modified Meguro staining were highly correlated with iron levels as detected by LA-ICP-MS (r2 â€‹= â€‹0.82, P â€‹< â€‹0.0001). Significant positive correlations were also found between LA-ICP-MS and the three quantitative MRI measurements: R2∗ (r2 â€‹= â€‹0.63), image phase (r2 â€‹= â€‹0.70) and QSM (r2 â€‹= â€‹0.74 (all p â€‹< â€‹0.0001)). R2∗ and QSM showed the strongest correlation with iron content; the correlation of phase with iron clearly showed increased variation, probably due to its high orientation dependence. Despite the obvious differences in iron distribution patterns within the cortex between AD patients and controls, no overall significant differences were found in iron as measured by LA-ICP-MS, nor in R2∗, phase or susceptibility. In conclusion, our results show that histochemistry as well as quantitative MRI methods such as R2∗ mapping and QSM provide reliable measures of iron distribution in the cortex. These results support the use of MRI studies focusing on iron distribution in both the healthy and the diseased brain.

Implementation and assessment of a likelihood ratio approach for the evaluation of LA-ICP-MS evidence in forensic glass analysis.

For the comparative analysis of glass fragments, a method using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is in use at the NFI, giving measurements of the concentration of 18 elements. An important question is how to evaluate the results as evidence that a glass sample originates from a known glass source or from an arbitrary different glass source. One approach is the use of matching criteria e.g. based on a t-test or overlap of confidence intervals. An important drawback of this method is the fact that the rarity of the glass composition is not taken into account. A similar match can have widely different evidential values. In addition the use of fixed matching criteria can give rise to a "fall off the cliff" effect. Small differences may result in a match or a non-match. In this work a likelihood ratio system is presented, largely based on the two-level model as proposed by Aitken and Lucy [1], and Aitken, Zadora and Lucy [2]. Results show that the output from the two-level model gives good discrimination between same and different source hypotheses, but a post-hoc calibration step is necessary to improve the accuracy of the likelihood ratios. Subsequently, the robustness and performance of the LR system are studied. Results indicate that the output of the LR system is robust to the sample properties of the dataset used for calibration. Furthermore, the empirical upper and lower bound method [3], designed to deal with extrapolation errors in the density models, results in minimum and maximum values of the LR outputted by the system of 3.1×10-3 and 3.4×104. Calibration of the system, as measured by empirical cross-entropy, shows good behavior over the complete prior range. Rates of misleading evidence are small: for same-source comparisons, 0.3% of LRs support a different-source hypothesis; for different-source comparisons, 0.2% supports a same-source hypothesis. The authors use the LR system in reporting of glass cases to support expert opinion in the interpretation of glass evidence for origin of source questions.

Multicomponent characterization and differentiation of flash bangers - Part II: Elemental profiling of plastic caps.

This study builds on the multicomponent analysis strategy for flash bangers which was previously introduced and where a representative sample set has been collected of a certain type of flash bangers. To expand the forensic strategy, elemental analysis of the plastic caps which are present in these items was performed. Both x-ray fluorescence (XRF) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis was performed to explore the possibilities for differentiation. The inherent inhomogeneity of the plastics resulted in high variations, especially for LA-ICP-MS trace analysis. In addition, due to the lack of suitable reference materials the LA-ICP-MS results can only be used for qualitative comparisons. Although XRF is less sensitive it allows for semi-quantitative analysis and the effect of inhomogeneity is significantly reduced due to the larger sample areas. Therefore, XRF is the method of choice for elemental analysis of intact plastic caps. In this scenario initial differentiation based on visual examination is combined with elemental analysis to obtain the highest degree of discrimination. In post-explosive scenarios, using XRF is not as straightforward due the irregular shapes of the burned plastic cap residues and contamination by explosive residues. For the analysis of these post-explosive caps, LA-ICP-MS proved to be useful for characterization and differentiation. Overall, it was found that blue caps contain a considerable higher amount of elements than the white caps, mainly due to additives related to the coloring process. This limits differentiation for the flash bangers containing white caps. Therefore, isotope ratio mass spectrometry (IRMS) analysis was performed to increase the differentiation potential. Based on carbon and hydrogen isotope ratios additional sets could be distinguished, both for flash bangers containing white and blue caps, that otherwise have similar visual and elemental characteristics. With the elemental and isotopic analysis of the plastic caps, an analysis strategy has been introduced that is not based on the pyrotechnic charge and therefore provides a unique opportunity to perform characterization and differentiation of flash bangers in pre- and post-explosive casework.

Forensic Comparison of Soil Samples Using Nondestructive Elemental Analysis.

Soil can play an important role in forensic cases in linking suspects or objects to a crime scene by comparing samples from the crime scene with samples derived from items. This study uses an adapted ED-XRF analysis (sieving instead of grinding to prevent destruction of microfossils) to produce elemental composition data of 20 elements. Different data processing techniques and statistical distances were evaluated using data from 50 samples and the log-LR cost (Cllr ). The best performing combination, Canberra distance, relative data, and square root values, is used to construct a discriminative model. Examples of the spatial resolution of the method in crime scenes are shown for three locations, and sampling strategy is discussed. Twelve test cases were analyzed, and results showed that the method is applicable. The study shows how the combination of an analysis technique, a database, and a discriminative model can be used to compare multiple soil samples quickly.

Isotopic and elemental profiling of ammonium nitrate in forensic explosives investigations.

Ammonium nitrate (AN) is frequently encountered in explosives in forensic casework. It is widely available as fertilizer and easy to implement in explosive devices, for example by mixing it with a fuel. Forensic profiling methods to determine whether material found on a crime scene and material retrieved from a suspect arise from the same source are becoming increasingly important. In this work, we have explored the possibility of using isotopic and elemental profiling to discriminate between different batches of AN. Variations within a production batch, between different batches from the same manufacturer, and between batches from different manufacturers were studied using a total of 103 samples from 19 different fertilizer manufacturers. Isotope-ratio mass spectrometry (IRMS) was used to analyze AN samples for their (15)N and (18)O isotopic composition. The trace-elemental composition of these samples was studied using inductively coupled plasma-mass spectrometry (ICP-MS). All samples were analyzed for the occurrence of 66 elements. 32 of these elements were useful for the differentiation of AN samples. These include magnesium (Mg), calcium (Ca), iron (Fe) and strontium (Sr). Samples with a similar elemental profile may be differentiated based on their isotopic composition. Linear discriminant analysis (LDA) was used to calculate likelihood ratios and demonstrated the power of combining elemental and isotopic profiling for discrimination between different sources of AN.