In this work, two deep subsurface wastewater infiltration systems (SWISs) were constructed and fed with domestic sewage (control system, S1) and mixed wastewater consisting of old landfill leachate and domestic sewage (experimental system, S2). S1 and S2 exhibited favorable removal efficiencies, with TP (98.8%, 98.7%), COD (87.6%, 86.9%), NH₄⁺-N (99.8%, 99.9%) and TN (99.2%, 98.9%). Even when increasing the pollutant load in S2 by adding old landfill leachate, the almost complete removal performance could be maintained in terms of low effluent concentrations and even increased in terms of load removal capabilities, which included COD (19.4, 25.9 g∙m⁻²·d⁻¹), NH₄⁺-N (8.2, 19.9 g∙m⁻²·d⁻¹), TN (8.9, 20.6 g∙m⁻²·d⁻¹). To investigate the transformation of dissolved organic matter along depth, Three-Dimensional Excitation Emission Matrix fluorescence spectroscopy combined with Fluorescence Regional Integration analysis was applied. The results showed that PⅠ,ₙ and PⅡ,ₙ (the proportions of biodegradable fractions) increased gradually from 6.59% to 21.8% at S2_20 to 10.8% and 27.7% at S2_110, but PⅢ,ₙ and PⅤ,ₙ (the proportions of refractory organics) declined from 23.1% to 27.8% at S2_20 to 21.1% and 16.4% at S2_110, respectively. In addition, high-throughput sequencing technology was employed to observe the bacterial community at different depths, and the predicted functional potential of the bacterial community was analyzed by PICRUSt. The results showed that the genera Flavobacterium, Pseudomonas, Vogesella, Acinetobacter and Aquabacterium might be responsible for refractory organic degradation and that their products might serve as the carbon source for denitrifiers to achieve simultaneous nitrate and refractory organic removal. PICRUSt further demonstrated that there was a mutual response between refractory organic degradation and denitrification. Overall, the combined treatment of domestic sewage and old leachate in rural areas by SWIS is a promising approach to achieve comprehensive treatment.

Dissolved organic matter (DOM) is recognized as a good indicator of water quality as its concentration is influenced by land use, rainwater, windborne material and anthropogenic activities. Recent technological advances make it possible to characterize fluorescent dissolved organic matter (FDOM), the fraction of DOM that fluoresces. Among these advances, portable fluorometers and benchtop fluorescence excitation and emission spectroscopy coupled with a parallel factor analysis (EEM-PARAFAC) have shown to be reliable. Despite their rising popularity, there is still a need to evaluate the extent to which these techniques can assess DOM dynamics at the watershed scale. We compare the performance of in-situ measurements of FDOM with laboratory measurements of fluorescence spectroscopy within the context of two distinct glacierized watersheds in Peru. Glacierized watersheds represent unique testing environments with contrasting DOM conditions, flowing from pristine, vegetation-free headwaters through locations with obvious anthropogenic influences. We used an in-situ fluorometer and a portable multimeter to take 38 measurements of FDOM, pH and turbidity throughout the two catchments. Additionally, samples were analyzed in the laboratory using the EEM-PARAFAC method. Results were compared to dissolved organic carbon (DOC) measurements using standard high-temperature catalytic oxidation. Our results show that the three techniques together were able to capture the DOM dynamics for both studied watersheds. Taken individually, all three methods allowed detection of the watershed DOM main points of sources but in a more limited way. Due to the narrow bandwidth of the portable fluorometer used in the study, FDOM measurements were almost non-detectable to protein-like substances. Indeed, the more demanding EEM-PARAFAC was able to both differentiate between potential sources of DOM and provide an estimate of relative concentrations of different organic components. Finally, similar to FDOM but to a lesser extent, the DOC measurements showed some limits where protein-like substances make up most of the DOM composition.

Cadmium (Cd) contamination of the soil is one of the most serious environmental problems of agricultural production. Phytoremediation has attracted increasing attention because it can safely remove the soil contaminates via plant uptake, accumulations and plant harvesting. However, the high Cd toxicity to plant tissues and treatment of the large amount of hazardous plant residues from phytoremediation have limited its commercial implementation. Here we show that the leaves of the tall fescue (Festuca arundinacea) can excrete Cd out to avoid Cd toxicity in plant tissues. Cd specific fluorescence spectroscopy with laser confocal scanning microscope, screening electron microscope with energy dispersive spectroscopy and guttation fluids analysis confirmed that leaf hydathodes were the pathway of Cd excretion in tall fescue. Element analysis showed that Cd was preferentially excreted out when compared to the ion nutrients. The amount of leaf Cd excretion was linearly increased in response to the Cd stress period. The phytoremediation efficiency was evaluated to remove 14.4% of soil Cd annually by the leaf Cd excretion in our experimental system. These findings indicate that a novel strategy of Cd phytoexcretion based on washing-off and collection of leaf surface Cd is feasible to avoid Cd toxic in plant tissues and the high treatment cost of hazardous plant residues.

Control of organic matter, nutrients and disinfection byproduct formation is a major challenge for the drinking water treatment plants on Matsu Islands, Taiwan, receiving source water from the eutrophic reservoirs. A pilot entrapped biomass reactor (EBR) system was installed as the pretreatment process to reduce organic and nitrogen contents into the drinking water treatment plant. The effects of hydraulic retention time (HRT) and combination of preceding physical treatment (ultraviolet and ultrasound) on the treatment performance were further evaluated. The results showed that the EBR system achieved higher than 81%, 35%, 12% and 46% of reduction in chlorophyll a (Chl a), total COD (TCOD), dissolved organic carbon (DOC) and total nitrogen (TN), respectively under varied influent concentrations. The treatment performance was not significantly influenced by HRT and presence/absence of physical pretreatment and the effluent water quality was stable; however, removal efficiencies and removal rates of Chl a, TCOD and DOC showed strong correlation with their influent concentrations. Excitation–emission matrix (EEM) fluorescence spectroscopy identified fulvic-like and humic-like substances as the two major components of dissolved organic matter (DOM) in the reservoir, and decreased intensity of the major peaks in effluent EEM fluorescence spectra suggested the effective removal of DOM without production of additional amount of soluble microbial products in the EBR. Through the treatment by EBR, about 10% of reduction of total trihalomethane formation potential for the effluent could also be achieved. Therefore, the overall results of this study demonstrate that EBR can be a potential pretreatment process for drinking water treatment plants receiving eutrophic source water.

This work evaluates the degradation of benzoic acid, a tracer from biomass burning, by different oxidation agents (Fe (III); H₂O₂; sunlight; and combinations of the previous ones) in model solutions and in real atmospheric waters. The extent of reactions was assessed by Ultraviolet–Visible and molecular fluorescence spectroscopies. The oxidation of benzoic acid occurred with the chemical oxidants Fe (III), H₂O₂, Fe (III) and H₂O₂ simultaneously in the presence of sunlight, and with Fe (III) and H₂O₂ simultaneously in the absence of light. The decrease of the pH value from neutral to acid for atmospheric waters generally increased the extent of oxidation. Sunlight was an important oxidation agent, and its combination with chemical oxidants increased the oxidation rate of benzoic acid, possibly due to the photogeneration of hydroxyl radicals. The results also suggested the occurrence of direct and indirect photolysis of benzoic acid in atmospheric waters. Moreover, the oxidation of benzoic acid produced new and more complex chromophoric compounds, which were then degraded. In addition, the nocturnal period is not sufficient for the full degradation of benzoic acid and of the intermediates formed by Fenton-like oxidation. The diurnal period may be enough for their full degradation through photo-Fenton-like oxidation, but this depends on the composition of the atmospheric waters, namely of the chromophoric content. Thus, this study highlights that benzoic acid from biomass burning, and its derivatives, may persist in atmospheric waters for periods of longer than one day, becoming available for other reactions, and may also affect the terrestrial and aquatic ecosystems through the wet depositions.

Widely used titanium dioxide (TiO2) nanoparticles are likely to accumulate ultimately in sediments and potentially pose a risk to water ecosystems. This study evaluated the effect of TiO2 nanoparticles on the photodissolution of particulate organic matter (POM) through fluorescence spectroscopy. Excitation-emission matrices and parallel factor analyses revealed that the fluorescent characteristics of produced dissolved organic matter (DOM) during photodissolution of suspended sediment and synthetic particulate organic matter (SPOM) were primarily humic-like. SPOM particles appeared to simulate well the photodissolution of suspended sediment. Quasi-complete increases in fluorescence intensity and chromophoric DOM (CDOM) abundance were reached after 90, 60, and 50 min irradiation for TiO2 concentrations of 0, 2, and 5 mg L−1, respectively. The faster increment of fluorescence intensity and CDOM abundance indicated the photocatalytic dissolution of SPOM, as opposite charges between TiO2 and SPOM at pH = 4 favored the adsorption of TiO2 onto SPOM. For sediments, the CDOM abundance and fluorescence intensity decreased with increasing TiO2 concentration, resulting from the photocatalytic degradation of photoproduced DOM from sediments. These results demonstrated that pH plays an important role in the photocatalytic dissolution of POM by TiO2. Therefore, appropriate pH controls should be implemented when TiO2 are used to treat sediments contaminated with organic pollutants. Finally, with increasing use of TiO2, its accumulation in sediments may affect the fate of carbon, nutrients, and heavy metals in shallow-water ecosystems.

The number of products containing engineered nanomaterials (ENMs) has increased due to their high industrial relevance as well as their use in diverse consumer products. At the end of their life cycle ENMs might be released to the environment and therefore concerns arise regarding their environmental impact. In order to track their fate upon disposal, it is crucial to establish methods to trace ENMs in complex environmental samples and to differentiate them from naturally-occurring nanoparticles. The goal of this study was to distinctively trace ENMs by (non-invasive) detection methods. For this, fluorescent ENMs, namely quantum dots (QDs), were distinctively traced in complex aqueous matrices, and were still detectable after a period of two months using fluorescence spectroscopy. In particular, two water-dispersible QD-species, namely CdTe/CdS QDs with N-acetyl-l-cysteine as capping agent (NAC-QDs) and surfactant-stabilized CdSe/ZnS QDs (Brij®58-QDs), were synthesized to examine their environmental fate during disposal as well as their potential interaction with naturally-occurring substances present in landfill leachates. When QDs were spiked into a leachate from an old landfill site, alteration processes, such as sorption, aggregation, agglomeration, and interactions with dissolved organic carbon (DOC), led to modifications of the optical properties of QDs. The spectral signatures of NAC-QDs deteriorated depending on residence time and storage temperature, while Brij®58-QDs retained their photoluminescence fingerprints, indicating their high colloidal stability. The observed change in photoluminescence intensity was mainly caused by DOC-interaction and association with complexing agents, such as fulvic or humic acids, typically present in mature landfill leachates. For both QD-species, the results also indicated that pH of the leachate had no significant impact on their optical properties. As a result, the unique spectroscopic fingerprints of QDs, specifically surfactant-stabilized QDs, allowed distinctive tracing in complex aqueous waste matrices in order to study their long-term behavior and ultimate fate.

The distribution of polycyclic aromatic hydrocarbons (PAHs) in the micro-zones of mangrove sediment is a predominant factors determining PAH bioavailability. In this study, a novel method for the in situ visualization (via microscope) and quantitative investigation of the PAH distribution in the micro-zones of mangrove sediment was established using microscopic fluorescence spectral analysis combined with derivative synchronous fluorescence spectroscopy (MFSA-DSFS). The MFSA-DSFS method significantly suppressed the background fluorescence signal of the sediment (the S/N values increased by over two orders of magnitude). The proportion of the nonpolar organic carbon content in the particulate organic matter (POM) rather than its content in the total organic matter (TOM) showed a significantly positive correlation with the uneven PAH distribution (Relative DC-M values) evaluated using the established method (p < 0.05). The extent of the uneven PAH distribution in the micro-zones of aged sediment was higher than that in the spiked sediment. Moreover, the distribution pattern of the PAHs within the mangrove sediment changed to become more homogeneous in the presence of low-molecular-weight organic acids (LMWOAs), which primarily contribute to increasing the POM content.

A novel method for in situ determination of the polycyclic aromatic hydrocarbons (PAHs) adsorbed onto the root surface of Kandelia obovata seedlings was established using laser-induced time-resolved nanosecond fluorescence spectroscopy (LITRF). The linear dynamic ranges for the established method were 1.5–1240ng/spot for phenanthrene, 1.0–1360ng/spot for pyrene and 5.0–1220ng/spot for benzo[a]pyrene. Then, the mechanisms of PAHs transport from the Ko root surface to tissues were investigated. The three-phase model including fast, slow and very slow fractions was superior to the single or dual-phase model to describe the PAHs transport processes. Moreover, the fast fraction of PAHs transport process was mainly due to passive movement, while the slow and very slow fractions were not. Passive movement was the main process of B[a]P adsorbed onto Ko root surface transport to tissues. In addition, the extent of the PAHs transport to Ko root tissues at different salinity were evaluated.