Comprehensive and heart-cutting multidimensional liquid chromatography-mass spectrometry and its applications in food analysis.

In food analysis, conventional one-dimensional liquid chromatography methods sometimes lack sufficient separation power due to the complexity and heterogeneity of the analysed matrices. Therefore, the use of two-dimensional liquid chromatography (2D-LC) turns out to be a powerful tool to consider, especially when coupled to mass spectrometry (MS). This review presents the most remarkable 2D-LC-MS food applications reported in the last 10 years, including a critical discussion of the multiple approaches, modulation strategies as well as the importance of the optimisation of the different analytical aspects that will condition the 2D-LC-MS performance. The presence of contaminants in food (food safety), the food quality and authenticity or the relationship between the beneficial effects of food and human health are some of the fields in which most of the 2D-LC-MS applications are mainly focused. Both heart-cutting and comprehensive applications are described and discussed in this review, highlighting the potential of 2D-LC-MS for the analysis of such complex samples.

Comprehensive and heart-cutting multidimensional liquid chromatography-mass spectrometry and its applications in food analysis.

In food analysis, conventional one-dimensional liquid chromatography methods sometimes lack sufficient separation power due to the complexity and heterogeneity of the analyzed matrices. Therefore, the use of two-dimensional liquid chromatography (2D-LC) turns out to be a powerful tool to consider, especially when coupled to mass spectrometry (MS). This review presents the most remarkable 2D-LC-MS food applications reported in the last 10 years, including a critical discussion of the multiple approaches, modulation strategies as well as the importance of the optimization of the different analytical aspects that will condition the 2D-LC-MS performance. The presence of contaminants in food (food safety), the food quality, and authenticity or the relationship between the beneficial effects of food and human health are some of the fields in which most of the 2D-LC-MS applications are mainly focused. Both heart-cutting and comprehensive applications are described and discussed in this review, highlighting the potential of 2D-LC-MS for the analysis of such complex samples.

Cross-Contamination of Residual Emerging Contaminants and Antibiotic Resistant Bacteria in Lettuce Crops and Soil Irrigated with Wastewater Treated by Sunlight/H2O2.

The sunlight/H2O2 process has recently been considered as a sustainable alternative option compared to other solar driven advanced oxidation processes (AOPs) in advanced treatment of municipal wastewater (WW) to be reused for crop irrigation. Accordingly, in this study sunlight/H2O2 was used as disinfection/oxidation treatment for urban WW treatment plant effluent in a compound parabolic collector photoreactor to assess subsequent cross-contamination of lettuce and soil by contaminants of emerging concern (CECs) (determined by QuEChERS extraction and LC-QqLIT-MS/MS analysis) and antibiotic resistant (AR) bacteria after irrigation with treated WW. Three CECs (carbamazepine (CBZ), flumequine (FLU), and thiabendazole (TBZ) at 100 µg L(-1)) and two AR bacterial strains (E. coli and E. faecalis, at 10(5) CFU mL(-1)) were spiked in real WW. A detection limit (DL) of 2 CFU mL(-1) was reached after 120 min of solar exposure for AR E. coli, while AR E. faecalis was more resistant to the disinfection process (240 min to reach DL). CBZ and TBZ were poorly removed after 90 min (12% and 50%, respectively) compared to FLU (94%). Lettuce was irrigated with treated WW for 5 weeks. CBZ and TBZ were accumulated in soil up to 472 ng g(-1) and 256 ng g(-1) and up-taken by lettuce up to 109 and 18 ng g(-1), respectively, when 90 min treated WW was used for irrigation; whereas no bacteria contamination was observed when the bacterial density in treated WW was below the DL. A proper treatment time (>90 min) should be guaranteed in order to avoid the transfer of pathogens from disinfected WW to irrigated crops and soil.

Chemical profiling of organic contaminants in rural surface waters combining target and non-target LC-HRMS/MS analysis.

The pollution of natural waters by contaminants of emerging concern (CECs) is one of the pressing problems due to their global distribution and potential negative effects on the environment and human health. In rural areas with lower population density and limited industrial development, less contamination is expected. However, the lack of wastewater treatment plants (WWTPs) or their poor removal efficiency can lead to significant input of pollutants. In this context, 11 streams of rural areas in the Guadalquivir River basin, southeast of Spain, were studied over two years to obtain an overview of the origin and distribution of contaminants. A target method using solid-phase extraction and liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) was developed for the analysis of 316 compounds in surface waters. A total of 78 target analytes were detected, comprising pesticides, pharmaceuticals, personal care products (PCPs), transformation products (TPs), and industrial chemicals. The flame retardant tributyl phosphate (16-3572 ng L-1) was detected in all samples, followed by caffeine (30-8090 ng L-1) and the analgesic tramadol (3-1493 ng L-1). The target approach was combined with a non-target analysis (NTA) strategy to obtain an overall perspective of the chemical profile of unexpected or unknown compounds in the samples. Up to 79 contaminants were tentatively identified, and 12 of them were finally confirmed with standards. Most of the contaminants determined by NTA were pharmaceuticals and their TPs. The results indicated that most of CECs have an urban origin despite traditional agriculture is the main economic activity in this region. Moreover, the absence of WWTPs in small towns is significant, as contamination levels at these sites were comparable to or higher than those in larger populations with sewage treatments.

Occurrence and risk assessment of pesticides and their transformation products related to olive groves in surface waters of the Guadalquivir river basin.

Pesticides are considered one of the main sources of contamination of surface waters, especially in rural areas highly influenced by traditional agricultural practices. The objective of this work was to evaluate the impact caused by pesticides and their transformation products (TPs) related to olive groves in surface waters with strong agricultural pressure. 11 streams were monitored during four sampling campaigns over 2 years. A solid-phase extraction, followed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) analysis was used in the quantitative target approach, with more than 70 validated compounds. Target method was combined with a suspect screening strategy involving more than 500 pesticides and TPs, using ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) to identify additional pesticides and TPs out of the scope of analysis. A total of 43 different compounds were detected with the target method. The herbicide MCPA was present in all samples and at the highest concentration (1260 ng L-1), followed by the fungicide carbendazim (1110 ng L-1), and the herbicide chlorotoluron (706 ng L-1). The suspect screening strategy revealed the presence of 7 compounds out of the target analysis (1 pesticide and 6 TPs). 6 analytes were confirmed with the analytical standards. Semi-quantification results revealed that TPs exhibited higher concentrations than their corresponding parent compounds, indicating higher persistency. Some small streams showed a comparable number of pesticides and concentrations to the most polluted large river. The determined pesticide and TPs concentrations represented an estimated environmental hazard in almost all sampling sites under study. This work underscores the importance of including pesticide TPs and small streams impacted by extensive agricultural activities in water quality monitoring programs.

Organic Microcontaminants in Tomato Crops Irrigated with Reclaimed Water Grown under Field Conditions: Occurrence, Uptake, and Health Risk Assessment.

In many regions, reuse of reclaimed water (RW) is a necessity for irrigation. The presence of organic microcontaminants (OMCs) in RW and their translocation to plants may represent a risk of human exposure. Nevertheless, information available about real field crops is scarce and focused on a limited number of compounds. The novelty of this work relies on the application of a wider-scope analytical approach based on a multianalyte target analysis (60 compounds) and a suspect screening (>1300 compounds). This methodology was applied to real field-grown tomato crops irrigated with RW. The study revealed the presence of 17 OMCs in leaves (0.04-32 ng g-1) and 8 in fruits (0.01-1.1 ng g-1), 5 of them not reported before in real field samples. A health-risk assessment, based on the toxicological threshold concern (TTC) concept, showed that RW irrigation applied under the conditions given does not pose any threat to humans.

TiO2 photocatalysis under natural solar radiation for the degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions at pilot plant scale.

This paper deals with the removal of two last-resort antibiotics, namely imipenem and meropenem, in aqueous solutions employing heterogeneous photocatalysis with TiO2 under natural solar radiation at pilot plant scale. It was found that TiO2 photocatalysis is a very efficient technique for the degradation of both compounds in aqueous solutions, albeit it's relatively low quantum efficiency. At the experimental conditions employed in the present work (compound parabolic collectors photoreactor) the optimal TiO2 concentration was about 50 mg L-1. Experiments conducted in various aqueous matrices lead to the conclusion that the method can be applied to real aqueous matrices, such as natural waters and wastewaters. The comparison of TiO2 photocatalysis and natural photolysis showed an important decrease of the accumulated energy required to achieve the complete removal of both antibiotics which, in terms of normalized illumination time (t30W), represented a reduction of 50 min for imipenem and 60 min for meropenem.

Photochemical degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions under solar radiation.

This paper deals with the photochemical fate of two representative carbapenem antibiotics, namely imipenem and meropenem, in aqueous solutions under solar radiation. The analytical method employed for the determination of the target compounds in various aqueous matrices, such as ultrapure water, municipal wastewater treatment plant effluents, and river water, at environmentally relevant concentrations, was liquid chromatography coupled with hybrid triple quadrupole-linear ion trap-mass spectrometry. The absorption spectra of both compounds were measured in aqueous solutions at pH values from 6 to 8, and both compounds showed a rather strong absorption band centered at about 300 nm, while their molar absorption coefficient was in the order from 9 × 103-104 L mol-1 cm-1. The kinetics of the photochemical degradation of the target compounds was studied in aqueous solutions under natural solar radiation in a solar reactor with compound parabolic collectors. It was found that the photochemical degradation of both compounds at environmentally relevant concentrations follows first order kinetics and the quantum yield was in the order of 10-3 mol einsten-1. Several parameters were studied, such as solution pH, the presence of nitrate ions and humic acids, and the effect of water matrix. In all cases, it was found that the presence of various organic and inorganic constituents in the aqueous matrices do not contribute significantly, either positively or negatively, to the photochemical degradation of both compounds under natural solar radiation. In a final set of photolysis experiments, the effect of the level of irradiance was studied under simulated solar radiation and it was found that the quantum yield for the direct photodegradation of both compounds remained practically constant by changing the incident solar irradiance from 28 to 50 W m-2.