A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO₂ nanoparticles and TiO₂/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO₂ and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO₂ and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

Laccases are capable of rapidly oxidizing benzo[a]pyrene. It is thought that the metabolites with an increase in water solubility caused by the oxidation of benzo[a]pyrene may stimulate the subsequent mineralization. However, to date, there has been no experimental evidence to support this. In this study, the fate of benzo[a]pyrene in soil affected by laccase amendment and the resulting soil bacterial responses were investigated. Laccase amendment promoted benzo[a]pyrene dissipation (15.6%) from soil, accompanied by trace mineralization (<0.58 ± 0.02%) and substantial bound residue formation (∼80%). An increase of ∼15% in the bound residue fraction was observed by laccase amendment, which mainly resulted from covalent binding of the residues to humin fraction. During the incubation, the abundance of bacterial 16S rRNA and polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase genes did not change markedly. In contrast, benzo[a]pyrene treated with laccase resulted in a smaller shift in the bacterial community composition, indicating a reduced disturbance to the soil microbial communities. These results here suggest that benzo[a]pyrene contaminated soil can be detoxified by laccase amendment mainly due to the enhanced bound residue formation to soil organic matter via covalent binding.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants in soil and are considered priority pollutants due to their carcinogenicity. Bioremediation of PAH-contaminated soils is often limited by the low solubility and strong sorption of PAHs in soil. Synthetic surfactants and biosurfactants have been used to enhance the bioavailability of PAHs and to accelerate microbial degradation. However, few studies have compared synthetic and biosurfactants in their efficiency in promoting PAH biodegradation in either native or bioaugmented soils. In this study, we evaluated mineralization of ¹⁴C-pyrene in soils with or without the augmentation of Mycobacterium vanbaalenii PYR-1, and characterized the effect of Brij-35 (synthetic) and rhamnolipid biosurfactant at different amendment rates. Treatment of rhamnolipid biosurfactant at 140 or 1400 μg surfactant g-dry soil⁻¹ rates resulted in a significantly longer lag period in ¹⁴C-pyrene mineralization in both native and bioaugmented soils. In contrast, amendment of Brij-35 generally increased ¹⁴C-pyrene degradation, and the greatest enhancement occurred at 21.6 or 216 μg surfactant g-dry soil⁻¹ rates, which may be attributed to increased bioavailability. Brij-35 and rhamnolipid biosurfactant were found to be non-toxic to M. vanbaalenii PYR-1 at 10X CMC, thus indicating rhamnolipid biosurfactant likely served as a preferential carbon source to the degrading bacteria in place of ¹⁴C-pyrene, leading to delayed and inhibited ¹⁴C-pyrene degradation. Mineralization of ¹⁴C-pyrene by M. vanbaalenii PYR-1 was rapid in the unamended soils, and up to 60% of pyrene was mineralized to ¹⁴CO₂ after 10 d in the unamended or Brij-35 surfactant-amended soils. Findings of this study suggest that application of surfactants may not always lead to enhanced PAH biodegradation or removal. If the surfactant is preferentially used as an easier carbon substrate than PAHs for soil microorganisms, it may actually inhibit PAH biodegradation. Selection of surfactant types is therefore crucial for the effectiveness of surfactant-aided bioremediation of PAH-contaminated soils.

This paper evaluates the UV photodegradation of 17β-estradiol (E2) on silica gel and in natural soil with different soil components. Silica gel was chosen as a stable and pure support to simulate the photochemical behavior of E2 on the surface of natural soil. Ultraviolet light, rather than visible light, was confirmed to play a decisive role in the photodegradation of E2 on silica gel. The effect of three soil components, including humic acid (HA), inorganic salts, and relative humidity (RH), on the photochemical behavior of E2 on silica gel or soil under UV irradiation was then evaluated. Two HA concentrations (10 and 20 mg g⁻¹) and three salts (ferric sulfate, copper sulfate and sodium carbonate) were observed to obviously inhibit the degradation of E2 on silica gel. Interestingly, nitrate was found to obviously improve the removal efficiency of E2. Both too-dry and too-wet conditions obviously reduced the removal rate of E2, and the optimum relative humidity (RH) value was found to be approximately about 35% (30 °C). Furthermore, twenty intermediate products and two major pathways were proposed to describe the transformation processes of E2 treated by UV irradiation, among which oligomers were found to be the major intermediate products before complete mineralization. The efficient UV removal of E2 on silica gel and natural soil suggested a feasible strategy to remediate E2 contaminated soil.

In this work we have investigated in details the process of degradation of the 4-amino-6-chlorobenzene-1,3-disulfonamide (ABSA), stable hydrolysis product of frequently used pharmaceutical hydrochlorothiazide (HCTZ), as one of the most ubiquitous contaminants in the sewage water. The study encompassed investigation of degradation by hydrolysis, photolysis, and photocatalysis employing commercially available TiO₂ Degussa P25 catalyst. The process of direct photolysis and photocatalytic degradation were investigated under different type of lights. Detailed insights into the reactive properties of HCTZ and ABSA have been obtained by density functional theory calculations and molecular dynamics simulations. Specifically, preference of HCTZ towards hydrolysis was confirmed experimentally and explained using computational study. Results obtained in this study indicate very limited efficiency of hydrolytic and photolytic degradation in the case of ABSA, while photocatalytic degradation demonstrated great potential. Namely, after 240 min of photocatalytic degradation, 65% of ABSA was mineralizated in water/TiO₂ suspension under SSI, while the nitrogen was predominantly present as NH4+. Reaction intermediates were studied and a number of them were detected using LC-ESI-MS/MS. This study also involves toxicity assessment of HCTZ, ABSA, and their mixtures formed during the degradation processes towards mammalian cell lines (rat hepatoma, H-4-II-E, human colon adenocarcinoma, HT-29, and human fetal lung, MRC-5). Toxicity assessments showed that intermediates formed during the process of photocatalysis exerted only mild cell growth effects in selected cell lines, while direct photolysis did not affect cell growth.

Shallow aquifers are the most accessible reservoirs of potable groundwater; nevertheless, they are also prone to various sources of pollution and it is usually difficult to distinguish between human and natural sources at the watershed scale. The area chosen for this study (the Campania Plain) is characterized by high spatial heterogeneities both in geochemical features and in hydraulic properties. Groundwater mineralization is driven by many processes such as, geothermal activity, weathering of volcanic products and intense human activities. In such a landscape, multivariate statistical analysis has been used to differentiate among the main hydrochemical processes occurring in the area, using three different approaches of factor analysis: (i) major elements, (ii) trace elements, (iii) both major and trace elements. The elaboration of the factor analysis approaches has revealed seven distinct hydrogeochemical processes: i) Salinization (Cl⁻, Na⁺); ii) Carbonate rocks dissolution; iii) Anthropogenic inputs (NO₃⁻, SO₄²⁻, U, V); iv) Reducing conditions (Fe²⁺, Mn²⁺); v) Heavy metals contamination (Cr and Ni); vi) Geothermal fluids influence (Li⁺); and vii) Volcanic products contribution (As, Rb). Results from this study highlight the need to separately apply factor analysis when a large data set of trace elements is available. In fact, the impact of geothermal fluids in the shallow aquifer was identified from the application of the factor analysis using only trace elements. This study also reveals that the factor analysis of major and trace elements can differentiate between anthropogenic and geogenic sources of pollution in intensively exploited aquifers.

Constructed coastal marsh regulates land-born nitrogen (N) loadings through salinity-dependent microbial N transformation processes. A hypothesis that salinity predominantly controls N removal in marsh was tested through incubation in a closed system with added-15NH4+ using sediments collected from five sub-marshes in Shihwa marsh, Korea. Time-course patterns of concentrations and 15N–atom% of soil-N pools were analyzed. Sediments having higher salinity and lower soil organic-C and acid-extractable organic-N exhibited slower rates of N mineralization and immobilization, nitrification, and denitrification. Rates of denitrification were not predicted well by sediment salinity but by its organic-C, indicating heterotrophic denitrification. Denitrification dominated N-loss from this marsh, and nitrogen removal capacity of this marsh was estimated at 337 kg N day−1 (9.9% of the daily N-loadings) considering the current rooting depth of common reeds (1.0 m). We showed that sediment N removal decreases with increasing salinity and can increase with increasing organic-C for heterotrophic denitrification.

Previous studies conducted on Daya Bay implied that the bay had been undergoing potential phosphorus limitation. In this context, alkaline phosphatase activity (APA) and the associated microbes were investigated in three different seasons in Daya Bay, South China Sea. Both bulk-community (fractioned into dissolved and particulate) and single-cell assays of APA were used to estimate the P status of phytoplankton at the community and species level. Unexpected high potential APA (Vmax) was observed in Daya Bay. Bulk APA showed that the maximum value in the spring (mean 583.26 nM h−1) corresponded well to low phosphate concentration. Furthermore, particulate APA (P-APA) showed an inverse hyperbolic relationship with phosphate, implying the coexistence of both constitutive and inducible AP; meanwhile, a threshold phosphate concentration for the transition from high to low APA was found around 0.2 μM in our study. P-APA and dissolved APA (D-APA) exhibited a tight link with phytoplankton and bacteria, which indicated that both of them were two main carriers of the enzyme. During the spring cruise, we encountered a small-scaled bloom of Gymnodinium that was probably at a declining phase. Extreme high levels of bulk and D-APA were characterized at this spring bloom event, and we suspected that bacteria especially active bacteria played an important role in APA production and partitioning at the post-bloom phase. In Daya Bay, diatoms were the dominant phytoplankton groups and percentages of ELF (Enzyme Labelled Fluorescence) labelled diatoms followed the same seasonal fluctuation as bulk APA, which suggested that diatoms were responsible for major variations of the bulk AP activity except for the spring bloom. Taken together, we considered that phytoplankton may be experiencing more P stress in spring and that the mineralization of organic P via alkaline phosphatase may help phytoplankton overcome P deficiency.

3D coupled modeling approach is used for the PCB dispersion assessment in the Gulf of Lion and its transfer to zooplankton via biogeochemical processes. PCB budgets and fluxes between the different species of PCB: dissolved, particulate, biosorbed on plankton, assimilated by zooplankton, which are governed by different processes: adsorption/desorption, bacteria and plankton mortality, zooplankton excretion, grazing, mineralization, volatilization have been estimated. Model outputs were compared with the available in situ data.It was found that the Rhone River outflows play an important role in the organism contamination in the coastal zone, whereas the atmospheric depositions are rather more important in the offshore zones. The transfer of the available contaminant to bacteria and phytoplankton species is mainly related to the biomass present in the water column. Absorption fluxes (grazing) to zooplankton are rather higher than the passive sorption fluxes, which are themselves also linked to the sorption coefficient.

Bioavailable dissolved organic carbon (BDOC), nitrogen (BDON) and their degradation rate constants were measured for the Chilika Lagoon, India. Long-term laboratory incubation experiments (90 days) were conducted at a constant temperature (25 °C) to quantify the bioavailable dissolved organic matter (DOM) and the possible degradation rate coefficients. The results showed that 41 ± 12% of dissolved organic carbon (DOC) and 47 ± 17% of dissolved organic nitrogen (DON) were BDOC and BDON respectively, with their stoichiometry found to be higher than the Redfield ratio. A first order exponential non-linear fitting routine was used to estimate pool sizes. The degradation rate constant (k) for the BDOC varied from 0.127–0.329 d−1 and BDON from 0.043–0.306 d−1 during the study period. Half-lives of the BDOC and BDON ranged from 2.1–5.4 and 2.2–15.9 days, respectively. Overall, the results showed that a fraction of the labile DON was transported from the lagoon to the adjacent coastal sea.