Advanced remediation in the presence of ferrous iron and carbonate-containing water by oxygen-induced oxidation of organic contaminants.

Mechanistic investigations of an environmentally friendly and easy-to-implement oxidation method in the remediation of contaminated anoxic waters, i.e. groundwater, through the sole use of oxygen for the oxygen-induced oxidation of pollutants were the focus of this work. This was achieved by the addition of O2 under anoxic conditions in the presence of ferrous iron which initiated the ferrous oxidation and the simultaneous formation of reactive •OH radicals. The involvement of inorganic ligands such as carbonates in the activation of oxygen as part of the oxidation of Fe2+ in water was investigated, too. The formation of •OH radicals, was confirmed in two different, indirect approaches by a fluorescence-based method involving coumarin as •OH scavenger and by the determination of the oxidation products of different aromatic VOCs. In the latter case, the oxidation products of several typical aromatic groundwater contaminants such as BTEX (benzene, toluene, ethylbenzene, xylenes), indane and ibuprofen, were determined. The influence of other ligands in the absence of bicarbonate and the effect of pH were also addressed. The possibility of activation of O2 in carbonate-rich water i.e. groundwater, may also potentially contribute to oxidation of groundwater contaminants and support other primary remediation techniques.

Elucidating the inhibitory effects of natural organic matter on the photodegradation of organic micropollutants: Atrazine as a probe compound.

Natural organic matter (NOM) is a complex mixture of heterogeneous compounds with varying functional groups and molecular sizes. Understanding the impact of NOM on the generation of photochemically produced reactive intermediates (PPRIs) and their potential inhibitory effects on photolysis has remained challenging due to the variations in the reactivities and concentrations of these functional groups. To address this gap, tannic acid (TA), gallic acid (GA), catechin (CAT), and tryptophan (Trp), were chosen as potential substitutes for NOM. Their effects on the photochemical transformation process were evaluated and compared with the widely used Suwannee River NOM (SRNOM). Atrazine (ATZ) was selected as a probe organic micropollutant (OMP). In this investigation, a significantly higher concentration of HO• was observed compared to O21, and the triplet excited state ( NOM*3). The findings suggest that the substituted phenols, particularly those with carboxylate-substitutions, played a substantial role in HO• formation, while electron-rich moieties acted as antioxidants, consuming NOM*3. Hydroxyl, carboxylic, and amino acid were the active groups for O21 formation. However, the inhibitory effects induced by the NOM surrogates were significant and mainly attributed to the direct photolysis inhibition caused by the inner filter effect. The scope of this work was further extended to include SRNOM, where similar trends with less pronounced formation of PPRIs and inner filter effects were observed. Therefore, this study sheds some light on the role of the functional groups in NOM during photochemical transformations of OMPs, thereby deepening our understanding of their fate in aqueous systems.

Ozonation of carbamazepine in the presence of sulfur-dopped graphene: Effect of process parameters and formation of main transformation products.

The stability of graphene structure in sulfur-doped graphene catalyst is demonstrated to be a key aspect during the ozonation process. Enhancing the stability of the sulfur-doped graphene structure is therefore important to improve its catalytic activity during the ozonation process. However, this has remained a challenge so far. Therefore, we adopted a low-energy microwave plasma technique to synthesize a high purity sulfur-doped graphene (S ⎯ Gr) catalyst for the ozonation process. The effect of S ⎯ Gr in the ozonation process was tested using carbamazepine (CBZ; 0.05 mM) as a probe compound. A complete CBZ removal was obtained at an ozone concentration of 0.08 mM while in comparison with single O3, ∼1.5 and 2.5 times decrease in the formation of the two important intermediate transformation products i.e., BQM (1-(2-benzaldehyde) - 4-hydroxy (1H, 3H)-quinazoline-2-one) and BQD (1-(2-benzaldehyde) - (1H, 3H)-quinazoline-2, 4-dione) was observed. Radical scavenging experiments confirmed the formation of HO. The XPS results showed that the activity of S ⎯ Gr towards the formation of HO was positively related to S-bearing carbon atoms at the edge of the graphene structure. Therefore, the addition of S ⎯ Gr is directly linked with the formation of HO, which further contributed to the improved elimination of intermediate transformation products. With a low sulfur loss of 1 %, the microwave plasma synthesized S ⎯ Gr catalyst remained stable during ozonation, implying its feasibility in practical application.

Aromatic amines leachate from cigarette butts into aquatic environments: Is there risk for water organisms?

There are many toxics, such as aromatic amines (AAs), in cigarette butts (CBs). As CBs are the most abundant litter worldwide, these chemicals may leach into water bodies. In the present work, for the first time, the levels of AAs leachates from CBs in distilled water (DW) and river water (RW) samples were evaluated at different exposure times ranging from 15 min to 30 days. The mean leachate levels of AAs in DW and RW samples were in the range of 0.2-566 and 0.2-596 ng L-1, respectively, with overall mean values of 569 and 556 ng L-1. There was no significant difference (p > 0.05) between the total AAs levels as well as the level of each examined AA in DW and RW samples. Aniline (ANL) had the highest leaching rate from CBs into water. The mean leachates of AAs from CBs into water were ranked as: ANL> 1-naphthylamine (1-NA)> 2-naphthylamine (2-NA) > 2,6-dimethylaniline (2, 6-DMA)> ∑toluidine (∑TOL)> o-anisidine (o-ASD)> ∑aminobiphenyl (∑ABP). Ecological risk assessment showed that ∑7AAs, ANL, p-TOL, o-TOL, 2-NA, and ∑ABP had medium risks to sensitive crustaceans and fish. As AAs are not the only hazardous chemicals which may leach from CBs into aquatic environments, restrictions on littering CBs into the environment are required due to the release of different toxics ultimately causing adverse effects on aquatic organisms.

Atmospheric pressure photoionization - High-field asymmetric ion mobility spectrometry (APPI-FAIMS) studies for on-site monitoring of aromatic volatile organic compounds (VOCs) in groundwater.

A continuously operating system for monitoring groundwater contamination by aromatic VOCs has been developed. For this purpose, a novel gas-water separation unit was to be used in combination with APPI-FAIMS. The gas-water separation unit successfully reduced the humidity in the sample flow to ≤1.6 ppmv prior to analyte ionization. Initially, toluene was selected as a model aromatic VOC. The quantitative response of toluene, as a single VOC in water (LOD <1 mg L-1), was used to investigate the feasibility of the monitoring system and the effect of humidity on the signal produced by the APPI-FAIMS. With humidity increase (up to 400 ppmv) an increase of the toluene signal for about 30% was observed, including the possible formation and detection of water clusters and toluene-water clusters. Similar effects were noted in the case of benzene. However, for the detection of single contaminants such as indane and trimethylbenzenes (TMBs) this was not observed even at relative high humidity (500 ppmv). Additionally, on-site, continuous, groundwater monitoring of the aromatic VOCs contamination was carried out successfully with the gas-water separation APPI-FAIMS at low humidity (0.3-1.6 ppmv) allowing simplified monitoring of a specific, total aromatic VOCs signal in groundwater.

Correction: Determining the role of redox-active materials during laser-induced water decomposition.

Correction for 'Determining the role of redox-active materials during laser-induced water decomposition' by Mark-Robert Kalus et al., Phys. Chem. Chem. Phys., 2019, 21, 18636-18651.

Determining the role of redox-active materials during laser-induced water decomposition.

Laser ablation in liquids (LAL) drives the decomposition of the liquid inducing the formation of a large number of different redox equivalents and gases. This not only leads to shielding effects and a decrease of the nanoparticle (NP) productivity but also can directly affect the NP properties such as the oxidation degree. In this study, we demonstrate that liquid decomposition during laser ablation in water is triggered by the redox activity of the 7 different bulk materials used; Au, Pt, Ag, Cu, Fe, Ti and Al, as well as by the reactivity of water with the plasma. Laser ablation of less-noble metals like aluminum leads to a massive gas evolution up to 390 cm3 per hour with molar hydrogen to oxygen ratios of 17.1. For more noble metals such as gold and platinum, water splitting induced by LAL is the dominant feature leading to gas volume formation rates of 10 up to 30 cm3 per hour and molar hydrogen to oxygen ratios of 1.2. We quantify the material-dependent ablation rate, shielding effects as well as the amount of hydrogen peroxide produced, directly affecting the yield and oxidation of the nanoparticles on the long-time scale.

Direct inlet probe ion mobility spectrometry.

Direct inlet probe (DIP) was used as an introduction and a pre-separation step for atmospheric pressure photoionization time-of-flight ion mobility spectrometry (APPI-TOF-IMS) for the first time. IMS is an analytical technique used to separate and identify ionized molecules in the gas phase and under atmospheric pressure based on their mobility. The utilization of DIP prior to IMS gives the possibility to introduce the analytes into the gas phase and provides an additional separation based on their vapor pressure. The proof-of-principle study was done on example of eight polycyclic aromatic hydrocarbons (PAHs) with the ring number from 2 to 5, namely naphthalene, fluorene, anthracene, phenanthrene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene. All these compounds are included in EPA priority pollutant list. Moreover, benzo[a]pyrene and benzo[k]fluoranthene are marked by EPA as probably carcinogen compounds and also included into SCF and EU lists. To increase the sensitivity of DIP-APPI-IMS the analysis was performed using a dopant assisted ionization method (benzene, 74mgL-1 in N2). It was found that the heating rate of the interface plays a crucial role for the whole analytical procedure. To prove the ability of this method to analyze PAHs in the mixture, the mixtures containing up to five PAHs were analyzed. The LODs for the analyzed compounds obtained with DIP-APPI-IMS were found to be in the tens- or hundreds-of-microgram-per-liter range. The obtained results are promising enough to ensure the potential of DIP as an introduction and a pre-separation step for ion mobility based methods.

Investigation of the Iron-Peroxo Complex in the Fenton Reaction: Kinetic Indication, Decay Kinetics, and Hydroxyl Radical Yields.

The Fenton reaction describes the reaction of Fe(II) with hydrogen peroxide. Several researchers proposed the formation of an intermediate iron-peroxo complex but experimental evidence for its existence is still missing. The present study investigates formation and lifetime of this intermediate at various conditions such as different Fe(II)-concentrations, absence vs presence of a hydroxyl radical scavenger (dimethyl sulfoxide, DMSO), and different pH values. Obtained results indicate that the iron-peroxo complex is formed under all experimental conditions. Based on these data, stability of the iron-peroxo complex could be examined. At pH 3 regardless of [Fe(II)]0 decay rates for the iron-peroxo complex of about 50 s-1 were determined in absence and presence of DMSO. Without DMSO and [Fe(II)]0 = 300 µM variation of pH yielded decay rates of about 70 s-1 for pH 1 and 2 and of about 50 s-1 at pH 3 and 4. Hence, the iron-peroxo complex becomes more stable with increasing pH. Furthermore, pH-dependent hydroxyl radical yields were determined to investigate whether the increasing stability of the intermediate complex may indicate a different reaction of the iron-peroxo complex which might yield Fe(IV) instead of hydroxyl radical formation as suggested in literature. However, it was found that hydroxyl radicals were produced proportionally to the Fe(II)-concentration.

Time-of-flight ion mobility spectrometry in combination with laser-induced fluorescence detection system.

A laser-induced fluorescence (LIF) was used as a complimentary detection system for time-of-flight ion mobility spectrometry (TOF-IMS). A LIF detection system is potentially faster than a conventional electrometer detector and can provide additional (to usual for IMS drift time) analytical information, namely wavelength of fluorescence maxima and fluorescence lifetime. Therefore, better discrimination ability can be expected. Additionally, the combination of IMS and LIF operates at atmospheric pressure. This allows fluorescence measurements of specified ions and ion clusters, which would not survive in a mass spectrometer. An IMS drift cell of open design with both the electrometer and LIF detectors was designed. The feasibility of IMS-LIF was demonstrated on the example of the Xanthene dye Rhodamine 6G (R6G). Electrospray was used as an ionization source. The release and desolvation of R6G ions from the electrospray with following IMS-LIF analysis were demonstrated. The effects of experimental parameters (e.g., ion gate and drift voltages, distance to ESI emitter) are demonstrated and discussed. The obtained results are promising enough to ensure the potential of LIF as a complimentary/alternative detection system for time-of-flight ion mobility spectrometry.

X-ray ionization differential ion mobility spectrometry.

X-ray was utilized as an ionization source for differential ion mobility spectrometry (DMS) for the first time. The utilization of this ionization source increases the potential of DMS system for on-site based applications. The influence of experimental parameters (e.g. accelerating voltage, filament current, and separation field) on the analysis of model compounds was investigated and discussed. It was found that both the positive and the negative reactive ion peaks [RIP(+) and RIP(-)] formed during X-ray ionization are identical with those observed with the traditional 63Ni radioactive ion source. This is especially notable for RIP(-), because the chemistry provided by other nonradioactive sources in the negative mode is more complicated or even different than that observed with a 63Ni source. Increase of either filament current or accelerating voltage resulted in increased intensity of both RIP(+) and RIP(-). However, because of the materials used for construction of X-ray adapter the maximal level of filament current and accelerating voltage used in this study were limited to 700mA and 5kV, respectively. Analytical performance was determined with two model compounds (acetone and methyl salicylate) using X-ray and directly compared to 63Ni ionization source. When X-ray was coupled to DMS, calculated LOD values were found to be within the range of 0.17-1.52ppbv/v (concentration in the carrier gas). These values are competitive with those calculated for DMS equipped with traditional 63Ni radioactive ionization source. The obtained results are promising enough to ensure the potential of X-ray as ionization source for DMS.

Low-temperature plasma ionization differential ion mobility spectrometry.

A low-temperature plasma (LTP) was used as an ionization source for differential ion mobility spectrometry (DMS) for the first time. This ionization source enhances the potential of DMS as a miniaturized system for on-site rapid monitoring. The effects of experimental parameters (e.g., discharge/carrier gas composition and flow rate, applied voltage) on the analysis of model aromatic compounds were investigated and discussed. It was found that the nature of reactant ion positive (RIP) is dependent on the discharge/carrier gas composition. The best response to the analyte was achieved when pure nitrogen was used as the discharge/carrier gas. The ability to perform analysis with zero helium consumption is especially attractive in view of the potential application of LTP-DMS for online (and on-site) monitoring. Analytical performance was determined with six environmentally relevant model compounds (benzene, toluene, ethylbenzene, p-xylene, 1,2,4-trimethylbenzene, and naphthalene) using LTP and directly compared to APPI and APCI ((63)Ni) ionization sources. When LTP was coupled to DMS, calculated LOD values were found to be in the range of 35-257 ng L(-1) (concentration in the carrier gas). These values are competitive with those calculated for two DMS equipped with traditional ionization sources (APPI, (63)Ni). The obtained results are promising enough to ensure the potential of LTP as ionization source for DMS.

Development of an electrospray-(63)Ni-differential ion mobility spectrometer for the analysis of aqueous samples.

The feasibility of an electrospray coupled with a (63)Ni-differential ion mobility spectrometer (DMS) for the analysis of water samples was proven on examples of 2-hexanone, fluoroacetamide, l-nicotine and 1-phenyl-2-thiourea water solutions. The model substances were selected in order to cover the vapor pressure range of 0.3-1467 Pa. To reduce the inline humidity, which demonstrates a strong influence on the analyte compensation voltage, two units with a desolvation region lengths of 15.5 and 7 mm were examined. The counter gas (heated to 100 °C nitrogen) with flow rates of 100 mL min(-1) and 30 mL min(-1) for short and long desolvation units, respectively, was essential for the efficient reduction of humidity. The reduction of water content in the carrier gas to 2.2-2.4 g m(-3) and to 1.8-2.0 g m(-3) for the short and long desolvation unit, respectively, was achieved at an electrospray flow rate of 1000 nL min(-1). With this adjusted experimental setup, the detection of model substances in the water solutions, in the range of 0.1-50 mg L(-1), was performed. No correlation between the vapor pressure and signal area was observed. The high stability of the inline humidity, and the correspondingly stable carrier gas flow rate, were found to be essential for an acceptable reproducibility.