Inês C. Santos

Recent advances and applications of gas chromatography vacuum ultraviolet spectroscopy

The vacuum ultraviolet spectrophotometer was developed recently as an alternative to existing gas chromatography detectors. This detector measures the absorption of gas-phase chemical species in the range of 120-240 nm, where all chemical compounds present unique absorption spectra. Therefore, qualitative analysis can be performed and quantification follows standard Beer-Lambert law principles. Different fields of application, such as petrochemical, food, and environmental analysis have been explored. Commonly demonstrated is the capability for facile deconvolution of co-eluting analytes. The concept of additive absorption for co-eluting analytes has also been advanced for classification and speciation of complex mixtures using a data treatment procedure termed time interval deconvolution. Furthermore, pseudo-absolute quantitation can be performed for system diagnosis, as well as potentially calibrationless quantitation. In this manuscript an overview of these features, the vacuum ultraviolet spectrophotometer instrumentation, and performance capabilities are given. A discussion of the applications of the vacuum ultraviolet detector is provided by describing and discussing the papers published thus far since 2014.

MALDI-TOF MS for the Identification of Cultivable Organic-Degrading Bacteria in Contaminated Groundwater near Unconventional Natural Gas Extraction Sites

Groundwater quality and quantity is of extreme importance as it is a source of drinking water in the United States. One major concern has emerged due to the possible contamination of groundwater from unconventional oil and natural gas extraction activities. Recent studies have been performed to understand if these activities are causing groundwater contamination, particularly with respect to exogenous hydrocarbons and volatile organic compounds. The impact of contaminants on microbial ecology is an area to be explored as alternatives for water treatment are necessary. In this work, we identified cultivable organic-degrading bacteria in groundwater in close proximity to unconventional natural gas extraction. Pseudomonas stutzeri and Acinetobacter haemolyticus were identified using matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry (MALDI-TOF MS), which proved to be a simple, fast, and reliable method. Additionally, the potential use of the identified bacteria in water and/or wastewater bioremediation was studied by determining the ability of these microorganisms to degrade toluene and chloroform. In fact, these bacteria can be potentially applied for in situ bioremediation of contaminated water and wastewater treatment, as they were able to degrade both compounds.

Screening of cadmium and lead in potentially contaminated waters using a spectrophotometric sequential injection lab-on-valve methodology.

The present work describes the development of a µSI-LOV method for the simultaneous screening of cadmium and lead in potentially contaminated water samples. To attain the biparametric determination, dithizone was chosen as the spectrophotometric reagent as it forms a colored complex with both metal ions, at different pH conditions. The cadmium determination was attained in strong alkaline conditions (pH≈12); the lead determination was calculated by the difference with the determination of both metals in mild alkaline conditions (pH≈8). The colored complex was measured at 550 nm and the method presented a LOD of 34 μg L(-1) for cadmium and 56 μg L(-1) for lead, with a sample consumption of 20 µL per assay and a determination rate of 55 h(-1). The results obtained were in agreement with those obtained by FAAS. The developed method was efficiently applied to the screening of cadmium and lead in marine port waters.

Sequential injection methodology for carbon speciation in bathing waters

A sequential injection method (SIA) for carbon speciation in inland bathing waters was developed comprising, in a single manifold, the determination of dissolved inorganic carbon (DIC), free dissolved carbon dioxide (CO2), total carbon (TC), dissolved organic carbon and alkalinity. The determination of DIC, CO2 and TC was based on colour change of bromothymol blue (660 nm) after CO2 diffusion through a hydrophobic membrane placed in a gas diffusion unit (GDU). For the DIC determination, an in-line acidification prior to the GDU was performed and, for the TC determination, an in-line UV photo-oxidation of the sample prior to GDU ensured the conversion of all carbon forms into CO2. Dissolved organic carbon (DOC) was determined by subtracting the obtained DIC value from the TC obtained value. The determination of alkalinity was based on the spectrophotometric measurement of bromocresol green colour change (611 nm) after reaction with acetic acid. The developed SIA method enabled the determination of DIC (0.24-3.5 mg C L(-1)), CO2 (1.0-10 mg C L(-1)), TC (0.50-4.0 mg C L(-1)) and alkalinity (1.2-4.7 mg C L(-1) and 4.7-19 mg C L(-1)) with limits of detection of: 9.5 μg C L(-1), 20 μg C L(-1), 0.21 mg C L(-1), 0.32 mg C L(-1), respectively. The SIA system was effectively applied to inland bathing waters and the results showed good agreement with reference procedures.

Use of solid phase extraction for the sequential injection determination of alkaline phosphatase activity in dynamic water systems

In this work, a solid phase extraction sequential injection methodology for the determination of alkaline phosphatase activity in dynamic water systems was developed. The determination of the enzymatic activity was based on the spectrophotometric detection of a coloured product, p-nitrophenol, at 405 nm. The p-nitrophenol is the product of the catalytic decomposition of p-nitrophenyl phosphate, a non-coloured substrate. Considering the low levels expected in natural waters and exploiting the fact of alkaline phosphatase being a metalloprotein, the enzyme was pre-concentrated in-line using a NTA Superflow resin charged with Zn(2+) ions. The developed sequential injection method enabled a quantification range of 0.044-0.441 unit mL(-1) of enzyme activity with a detection limit of 0.0082 unit mL(-1) enzyme activity (1.9 μmol L(-1) of pNP) and a determination rate of 17 h(-1). Recovery tests confirmed the accuracy of the developed sequential injection method and it was effectively applied to different natural waters and to plant root extracts.

Characterization of bacterial diversity in contaminated groundwater using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Groundwater is a major source for drinking water in the United States, and therefore, its quality and quantity is of extreme importance. One major concern that has emerged is the possible contamination of groundwater due to the unconventional oil and gas extraction activities. As such, the impacts of exogenous contaminants on microbial ecology is an area to be explored to understand what are the chemical and physical conditions that allow the proliferation of pathogenic bacteria and to find alternatives for water treatment by identifying organic-degrading bacteria. In this work, we assess the interplay between groundwater quality and the microbiome in contaminated groundwaters rich in hydrocarbon gases, volatile organic and inorganic compounds, and various metals. Opportunistic pathogenic bacteria, such as Aeromonas hydrophila, Bacillus cereus, Pseudomonas aeruginosa, and Stenotrophomonas maltophilia, were identified, increasing the risk for consumption of and exposure to these contaminated groundwaters. Additionally, antimicrobial tests revealed that many of the identified bacteria were resistant to different antibiotics. The MALDI-TOF MS results were successfully confirmed with 16S rRNA gene sequencing, proving the accuracy of this high-throughput method. Collectively, these data provide a seminal understanding of the microbial populations in contaminated groundwater overlying anthropogenic activities like unconventional oil and gas development.

Sequential injection system exploring the standard addition method for phosphate determination in high salinity samples: interstitial, transitional and coastal waters

A sequential injection system for phosphate determination within a wide concentration range was developed for water samples with high salinity levels. The determination is based on molybdenum blue chemistry using the standard addition quantification method. The detection system included a multi-reflective flow cell coupled to a light emitting diode, enabling the minimization of the schlieren effect. The developed system gave a LOD of 0.3 μmol P L−1 and LOQ of 1.1 μmol P L−1 with a sample consumption of 125 μL. A determination rate of about 30 h−1 was obtained, and the developed method was effectively applied to interstitial, transitional and coastal waters.

Development of flow injection potentiometric methods for the off-line and on-line determination of fluoride to monitor the biodegradation of a monofluorophenol in two bioreactors.

Water treatment has become a source of concern as new pollutants and higher volumes of waste water must be treated. Emerging biological approaches, namely the use of bioreactors, for cleaning processes have been introduced. The use of bioreactors requires the development of efficient monitoring tools, preferably with real-time measurements. In this work, a couple of flow injection systems were developed and optimized for the potentiometric determination of fluoride to monitor a rotating biological contactor (RBC) bioreactor and a sequencing batch reactor (SBR) with off-line and on-line sampling. Both the RBC and the SBR bioreactors were set up for the biodegradation of the halogenated organic compound 2-fluorophenol and, as fluoride was a degradation byproduct, the process was monitored by following up its concentration. The described flow injection potentiometric methods enabled the fluoride determination within the required quantification range 0.10-100mM. The possible interferences from the growth medium were minimized in-line. The determination rate was 78 h(-1) for the off-line monitoring of RBC and 50(-1)h for the on-line monitoring of the SBR, with a sample consumption of 0.500 mL and 0.133 mL per determination, respectively. Furthermore, the overall reagent consumption was quite low. The accuracy of the system was evaluated by comparison with a batch procedure. The SBR efficiency was monitored both on-line by the flow system and off-line by HPLC, for comparison purposes.

Exploring the links between groundwater quality and bacterial communities near oil and gas extraction activities

Bacterial communities in groundwater are very important as they maintain a balanced biogeochemical environment. When subjected to stressful environments, for example, due to anthropogenic contamination, bacterial communities and their dynamics change. Studying the responses of the groundwater microbiome in the face of environmental changes can add to our growing knowledge of microbial ecology, which can be utilized for the development of novel bioremediation strategies. High-throughput and simpler techniques that allow the real-time study of different microbiomes and their dynamics are necessary, especially when examining larger data sets. Matrix-assisted laser desorption-ionization (MALDI) time-of-flight mass spectrometry (TOF-MS) is a workhorse for the high-throughput identification of bacteria. In this work, groundwater samples were collected from a rural area in southern Texas, where agricultural activities and unconventional oil and gas development are the most prevalent anthropogenic activities. Bacterial communities were assessed using MALDI-TOF MS, with bacterial diversity and abundance being analyzed with the contexts of numerous organic and inorganic groundwater constituents. Mainly denitrifying and heterotrophic bacteria from the Phylum Proteobacteria were isolated. These microorganisms are able to either transform nitrate into gaseous forms of nitrogen or degrade organic compounds such as hydrocarbons. Overall, the bacterial communities varied significantly with respect to the compositional differences that were observed from the collected groundwater samples. Collectively, these data provide a baseline measurement of bacterial diversity in groundwater located near anthropogenic surface and subsurface activities.

Application of Mid- and Near-Infrared Spectroscopy for the Control and Chemical Evaluation of Brine Solutions and Traditional Sea Salts

Mid- and near-infrared spectroscopy methodologies were explored for the analysis of brine solutions and traditional sea salt samples. Brine solutions from different salt pans, corresponding to different stages of sodium chloride crystallisation, were collected. A total of 61 dried and non-dried traditional sea salts were also analysed. Partial least squares regression with leave-one-out cross-validation strategy was applied for the calibration of inorganic constituents Ca2+, Mg2+ and K+, alkalinity as HCO3−, SO42−, NO2− and NO3− and phosphate in brine solutions. Promising results were obtained with the near-infrared (NIR) methodology for brine solutions with coefficients of determination R2 > 0.90 for Mg+2, K+, HCO3− and SO42−. Using mid-infrared, the calibration for H2PO4− was R2 = 0.85. In relation to the sea salt samples, the strategy adopted was the re-sampling based cross-validation using different spectral pre-processing treatments. In this case, the calibrations using the two IR methodologies fell bellow acceptable levels for the techniques; however, by comparing the R2 coefficient, the results were slightly better when using the NIR spectra of dried sea samples. In general, these results open a new possibility for the IR applications and also bring an opportunity for continuing with the NIR characterization for dried sea salt samples.