An Automated Methodology for Non-targeted Compositional Analysis of Small Molecules in High Complexity Environmental Matrices Using Coupled Ultra Performance Liquid Chromatography Orbitrap Mass Spectrometry

Abstract

The life-critical matrices of air and water are among the most complex chemical mixtures that are ever encountered. Ultrahigh-resolution mass spectrometers, such as the Orbitrap, provide unprecedented analytical capabilities to probe the molecular composition of such matrices, but the extraction of non-targeted chemical information is impractical to perform via manual data processing. Automated non-targeted tools rapidly extract the chemical information of all detected compounds within a sample dataset. However, these methods have not been exploited in the environmental sciences. Here, we provide an automated and (for the first time) rigorously tested methodology for the non-targeted compositional analysis of environmental matrices using coupled liquid chromatography–mass spectrometric data. First, the robustness and reproducibility was tested using authentic standards, evaluating performance as a function of concentration, ionization potential, and sample complexity. The method was then used for the compositional analysis of particulate matter and surface waters collected from worldwide locations. The method detected >9600 compounds in the individual environmental samples, arising from critical pollutant sources, including carcinogenic industrial chemicals, pesticides, and pharmaceuticals among others. This methodology offers considerable advances in the environmental sciences, providing a more complete assessment of sample compositions while significantly increasing throughput.

Technical note: Effects of storage conditions on molecular-level composition of organic aerosol particles

“…In order to reduce the large number of total features detected and remove potential interferences from non-informative noise and background peaks, a peak intensity filter was set to 7E5, hence only features with a peak intensity higher than this value were considered for further analysis. This led to 4735 features being detected for each of the 270 β-pinene SOA samples analyzed (excluding blanks); this figure is comparable to previous studies, with a similar number of features being detected in ambient PM2.5 samples using LC-MS characterization (Pereira et al, 2021).…”

Technical note: Effects of storage conditions on molecular-level composition of organic aerosol particles

“…In order to reduce the large number of total features detected and remove potential interferences from non-informative noise and background peaks, a peak intensity filter was set to 7E5, hence only features with a peak intensity higher than this value were considered for further analysis. This led to 4735 features being detected for each of the 270 β-pinene SOA samples analyzed (excluding blanks); this figure is comparable to previous studies, with a similar number of features being detected in ambient PM2.5 samples using LC-MS characterization (Pereira et al, 2021).…”

The Potential of Sewage Sludge to Predict and Evaluate the Human Chemical Exposome

“…Low levels (up to 0.4 ng/mL) of the insect repellent N,N-diethyl-3-methylbenzamide (DEET) were also determined in 40% of the serum samples. This chemical is commonly used in our study area, and its presence has been previously reported in both human (at similar levels, ≈3.2 ng/mL in maternal blood) and environmental samples including air and drinking water . High levels of the disinfectant Benzododecinium (up to 118 ng/g (placenta) and 86 ng/mL (serum)) were detected in greater than 60% of the samples.…”

“…This chemical is commonly used in our study area, and its presence has been previously reported in both human (at similar levels, ≈3.2 ng/mL in maternal blood) 52 and environmental samples including air and drinking water. 53 High levels of the disinfectant Benzododecinium (up to 118 ng/g (placenta) and 86 ng/mL (serum)) were detected in greater than 60% of the samples. This chemical is present in products such as Sterinol, widely used as disinfectant before and during the wake of the COVID-19 pandemic 46 and have been found to cross skin with intensive usage, reaching levels in plasma of up to 141.2 ng/L after an intensive five day usage.…”

Composition and metabolic potential of microbial communities in chemically contaminated soils: a multi-dimensional assessment

“…Therefore, the contaminated soil sample collection locations involved seven sites with different climatic conditions to provide more comprehensive environmental information, and their detailed pollution characteristics are shown in Figure 1 , Supplementary Table S1 , and Supplementary Figure S1 . The peak areas in spectral analysis were used as semi-quantitative indicators to compare the relative abundance of pollutants across different samples ( Pereira et al, 2021 ). Non-targeted screening results of soil samples from different contaminated sites by GC-MS and HPLC-HRMS are shown in Supplementary Table S2 .…”

Technical note: Effects of storage conditions on molecular-level composition of organic aerosol particles

“…In order to reduce the large number of total features detected and remove potential interferences from non-informative noise and background peaks, a peak intensity filter was set to 7E5, hence only features with a peak intensity higher than this value were considered for further analysis. This led to 4735 features being detected for each of the 270 β-pinene SOA samples analyzed (excluding blanks); this figure is comparable to previous studies, with a similar number of features being detected in ambient PM2.5 samples using LC-MS characterization (Pereira et al, 2021).…”

The Potential of Sewage Sludge to Predict and Evaluate the Human Chemical Exposome

“…Low levels (up to 0.4 ng/mL) of the insect repellent N,N-diethyl-3-methylbenzamide (DEET) were also determined in 40% of the serum samples. This chemical is commonly used in our study area, and its presence has been previously reported in both human (at similar levels, ≈3.2 ng/mL in maternal blood) and environmental samples including air and drinking water . High levels of the disinfectant Benzododecinium (up to 118 ng/g (placenta) and 86 ng/mL (serum)) were detected in greater than 60% of the samples.…”

“…This chemical is commonly used in our study area, and its presence has been previously reported in both human (at similar levels, ≈3.2 ng/mL in maternal blood) 52 and environmental samples including air and drinking water. 53 High levels of the disinfectant Benzododecinium (up to 118 ng/g (placenta) and 86 ng/mL (serum)) were detected in greater than 60% of the samples. This chemical is present in products such as Sterinol, widely used as disinfectant before and during the wake of the COVID-19 pandemic 46 and have been found to cross skin with intensive usage, reaching levels in plasma of up to 141.2 ng/L after an intensive five day usage.…”

Composition and metabolic potential of microbial communities in chemically contaminated soils: a multi-dimensional assessment

“…Therefore, the contaminated soil sample collection locations involved seven sites with different climatic conditions to provide more comprehensive environmental information, and their detailed pollution characteristics are shown in Figure 1 , Supplementary Table S1 , and Supplementary Figure S1 . The peak areas in spectral analysis were used as semi-quantitative indicators to compare the relative abundance of pollutants across different samples ( Pereira et al, 2021 ). Non-targeted screening results of soil samples from different contaminated sites by GC-MS and HPLC-HRMS are shown in Supplementary Table S2 .…”

Technical note: Effects of storage conditions on molecular-level composition of organic aerosol particles

“…In order to reduce the large number of total features detected and remove potential interferences from non-informative noise and background peaks, a peak intensity filter was set to 7E5, hence only features with a peak intensity higher than this value were considered for further analysis. This led to 4735 features being detected for each of the 270 β-pinene SOA samples analyzed (excluding blanks); this figure is comparable to previous studies, with a similar number of features being detected in ambient PM2.5 samples using LC-MS characterization (Pereira et al, 2021).…”

The Potential of Sewage Sludge to Predict and Evaluate the Human Chemical Exposome

“…Low levels (up to 0.4 ng/mL) of the insect repellent N,N-diethyl-3-methylbenzamide (DEET) were also determined in 40% of the serum samples. This chemical is commonly used in our study area, and its presence has been previously reported in both human (at similar levels, ≈3.2 ng/mL in maternal blood) and environmental samples including air and drinking water . High levels of the disinfectant Benzododecinium (up to 118 ng/g (placenta) and 86 ng/mL (serum)) were detected in greater than 60% of the samples.…”

“…This chemical is commonly used in our study area, and its presence has been previously reported in both human (at similar levels, ≈3.2 ng/mL in maternal blood) 52 and environmental samples including air and drinking water. 53 High levels of the disinfectant Benzododecinium (up to 118 ng/g (placenta) and 86 ng/mL (serum)) were detected in greater than 60% of the samples. This chemical is present in products such as Sterinol, widely used as disinfectant before and during the wake of the COVID-19 pandemic 46 and have been found to cross skin with intensive usage, reaching levels in plasma of up to 141.2 ng/L after an intensive five day usage.…”

Composition and metabolic potential of microbial communities in chemically contaminated soils: a multi-dimensional assessment

“…Therefore, the contaminated soil sample collection locations involved seven sites with different climatic conditions to provide more comprehensive environmental information, and their detailed pollution characteristics are shown in Figure 1 , Supplementary Table S1 , and Supplementary Figure S1 . The peak areas in spectral analysis were used as semi-quantitative indicators to compare the relative abundance of pollutants across different samples ( Pereira et al, 2021 ). Non-targeted screening results of soil samples from different contaminated sites by GC-MS and HPLC-HRMS are shown in Supplementary Table S2 .…”