RESUMEN

Wastewater surveillance is an effective and objective approach to monitor contaminant releases and drug usage in the catchment, the estimation requires accurate measurement. In this study, a novel diffusive gradients in thin-film (DGT) technique based on molecularly imprinted polymers (MIPs) for selective measurement of a class of widely prescribed cardiovascular drugs (ß-blockers) in wastewater was developed. The synthesized MIPs showed strong affinity and selectivity for the target compounds. The MIP-DGT had large effective capacities, its performance was independent of a wide range of environmental conditions, including pH (4.58 - 8.89), ionic strength (0.01 - 0.5 M) and dissolved organic matter (< 20 mg L-1). Biofouling had little effect on the uptake of target compounds within 7 days. MIP-DGT devices were applied in a Chinese urban WWTP alongside an auto-sampler. Metoprolol concentrations detected were much higher than other ß-blockers. Concentrations obtained using MIP-DGT were comparable to the 24 h composite samples using an autosampler. The estimated daily consumption calculated based on the data obtained with MIP-DGT implied that metoprolol and propranolol were the most popular ß-blockers in the studied area. Overall, the results in this study demonstrate that the MIP-DGT is a cost-effective, reliable and efficient tool for in situ wastewater monitoring.

RESUMEN

The occurrence and risk of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-Q), derived from the oxidation of the tire antidegradant 6PPD, has raised significant concern since it was found to cause acute mortality in coho salmon when exposed to urban runoff. Given the short half-life period and low solubility of 6PPD-Q, reliable in situ measurement techniques are required to accurately understand its occurrence and behaviour in aquatic environments. Here, using the diffusive gradients in thin-films (DGT) method with HLB as a binding agent, we developed a new methodology to measure 6PPD-Q in urban waters. 6PPD-Q was rapidly and strongly adsorbed on the HLB-binding gel and was efficiently extracted using organic solvents. The HLB-DGT accumulated 6PPD-Q linearly for >7 d and its performance was not significantly affected by pH (6.5-8.5), ionic strength (0.0001-0.5 M) or dissolved organic matter (0-20 mg L-1). Field evaluation of the DGT method demonstrated its effectiveness in urban runoff, detecting 6PPD-Q levels of 15.8-39.5 ng L-1 in rivers. In snowmelt, DGT detected 6PPD-Q levels of 210 ng L-1 which is two times higher than the value obtained by grab sampling. 6PPD-Q levels were much higher in snowmelt than those in rivers. This indicates that snowfall constitutes an important transport pathway for 6PPD-Q and that DGT effectively captured the fraction continuously released from dust particles in the snow samples. 6PPD-Q posed a substantial risk to migratory fish in urban waters, and its release from tire wear particles requires further investigation. This study is the first to develop a DGT-based method for 6PPD-Q determination in urban waters, and the method can ensure an accurate measurement of the release of 6PPD-Q to the environment, particularly in rainfall or snowmelt, important pathways for its entry into the aquatic environment.

RESUMEN

Diffusive gradients in thin films (DGTs) have been well-documented for the measurement of a broad range of organic pollutants in surface water. However, the performance has been challenged by the inherent periodic concentration fluctuations for most organic pollutants. Therefore, there is an urgent need to assess the true time-weighted average (TWA) concentration based on fluctuating concentration profiles. The study aimed to evaluate the responsiveness of DGT and accuracy of TWA concentrations, considering various concentration fluctuating scenarios of 20 pharmaceuticals in surface water. The reliability and accuracy of the TWA concentrations measured by the DGT were assessed by comparison with the sum of cumulative mass of DGT exposed at different stages over the deployment period. The results showed that peak concentration duration (1-5 days), peak concentration fluctuation intensity (6-20 times), and occurrence time of peak concentration fluctuation (early, middle, and late stages) have minimal effect on DGT's response to most target pharmaceutical concentration fluctuations (0.8 < CDGT/CTWA < 1.2). While the downward-bent accumulations of a few pharmaceuticals on DGT occur as the sampling time increases, which could be accounted for by capacity effects during a long-time sampling period. Additionally, the DGT device had good sampling performance in recording short fluctuating concentrations from a pulse event returning to background concentrations with variable intensity and duration. This study revealed a satisfactory capacity for the evaluation of the TWA concentration of pharmaceuticals integrated over the period of different pulse deployment for DGT, suggesting that this passive sampler is ideally suited as a monitoring tool for field application. This study represents the first trial for evaluating DGT sampling performance for pharmaceuticals with multiple concentration fluctuating scenarios over time, which would be valuable for assessing the pollution status in future monitoring campaign.

Asunto(s)

RESUMEN

Polycyclic aromatic hydrocarbons (PAHs) are priority pollutants and need to be measured reliably in waters and other media, to understand their sources, fate, behaviour and to meet regulatory monitoring requirements. Conventional water sampling requires large water volumes, time-consuming pre-concentration and clean-up and is prone to analyte loss or contamination. Here, for the first time, we developed and validated a novel diffusive gradients in thin-films (DGT) passive sampler for PAHs. Based on the well-known DGT principles, the sampler pre-concentrates PAHs with typical deployment times of days/weeks, with minimal sample handling. For the first time, DGT holding devices made of metal and suitable for sampling hydrophobic organic compounds were designed and tested. They minimize sorption and sampling lag times. Following tests on different binding layer resins, a MIP-DGT was preferred - the first time applying MIP for PAHs. It samples PAHs independent of pH (3.9 -8.1), ionic strength (0.01 -0.5 M) and dissolved organic matter < 20 mg L-1, making it suitable for applications across a wide range of environments. Field trials in river water and wastewater demonstrated that DGT is a convenient and reliable tool for monitoring labile PAHs, readily achieving quantitative detection of environmental levels (sub-ng and ng/L range) when coupled with conventional GC-MS or HPLC. ENVIRONMENTAL IMPLICATIONS: PAHs are carcinogenic and genotoxic compounds. They are environmentally ubiquitous and must be monitored in waters and other media. This study successfully developed a new DGT passive sampler for reliable in situ time-integrated measurements of PAHs in waters at the ng/L level. This is the first time to use passive samplers for accurate measurements of hydrophobic organic contaminants in aquatic systems without calibration, a big step forward in monitoring PAHs. The application of this new sampler will enhance our understanding of the sources, fate, behavior and ecotoxicology of PAHs, enabling improved environmental risk assessment and management of these compounds.

Asunto(s)

RESUMEN

Dissolved sulfide in sediment porewater significantly influences aquatic ecosystems. Conventionally, sulfide determination in sediment porewater relies on ex-situ analytical methods, susceptible to measurement errors due to sulfide oxidation and volatilization during sample analysis. In this study, we introduced an innovative in-situ method for assessing dissolved sulfide in surface sediment porewater, leveraging the integration of diffusive gradients in thin films (DGT) with digital imaging. The DGT device effectively concentrates sulfide in sediment porewater, inducing observable color changes in the binding gel. Recordings of these changes, captured by imaging equipment, facilitated the establishment of calibration curves correlating grayscale value alterations in the binding gel to sulfide concentrations. Under optimal conditions, the developed method demonstrated a linear detection range of 3.0-200 µmol L-1 at 20 °C, particularly when the exposure time exceeded 180 min. The developed method is insensitive to salinity and suitable for measuring sulfide concentrations in various natural water environments. Compared to traditional ex-situ methods, our approach circumvents challenges linked to intricate pre-treatment, prolonged analysis duration, and significant systemic errors. This proposed method presents a real-time solution for sulfide concentration assessment in surface sediment porewater, empowering researchers with an efficient means to monitor and study dynamic sulfide levels.

RESUMEN

Atmospheric deposition is an important source of heavy metal in agricultural soils, but there is limited research on the mobility of these metals in soil and their impact on soil amendment. Here, we performed a dust incubation experiment in soils in the laboratory and a factorial transplant experiment at three field sites with a gradient of atmospheric deposition to examine the impacts of atmospherically deposited heavy metals (Cu, Cd, and Pb) on the mobility and bioavailability in soils with and without lime applications. Results showed that the atmospherically deposited heavy metals showed high mobility and were primarily presented in the soluble ionic fractions in the wet part and acid-exchangeable and reducible fractions in the dry part of atmospheric deposition. Atmospheric dust addition caused the 2p3/2 and 2p1/2 electrons of Cu atoms in uncontaminated soils to transition the 3d vacant states, resulting in similar copper absorption peaks as atmospheric particles by the observation of X-ray absorption near-edge spectroscopy (XANES). In the field, atmospheric deposition can only increase the mobile fractions in the surface soils, but not in the deeper layers. However, the deposition can increase the soluble and diffusive gradients in thin films (DGT)-measured bioavailable fractions in profile along with the soil depth. Lime applications cannot significantly reduce the mobile fractions of heavy metals in the surface soils exposed to atmospheric deposition, but significantly reduce the heavy metal concentrations in soil solutions and the DGT-measured bioavailable concentrations, particularly in the deeper layer (6-10 cm). The major implication is that atmospherically deposited heavy metals can significantly increase their bioavailable concentrations in the plough horizon of soil and constrain the effects of soil amendments on heavy metal immobilization, thereby increasing the risks of crop uptake.

RESUMEN

Cadmium (Cd) activation, especially at a high spatial resolution, in paddy soils with a high geogenic Cd background is yet to be understood. To investigate the temporal and spatial patterns of Cd activation in rice rhizosphere, pot and rhizotron experiments were conducted using four paddy soils with high geogenic Cd (0.11-3.70 mg kg-1) from Guangxi, southwestern China. The pot experiment results showed that porewater Cd concentrations initially decreased and then increased over the complete rice growth period, reaching its lowest value during the late-tillering and early-filling stages. Besides, correlation analysis identified organic matter and root manganese (Mn) content as the main factors affecting rice Cd uptake, with Mn having a negative effect and organic matter having a positive effect. Sub-millimeter two-dimensional chemical imaging revealed that the distribution of labile Cd in the rhizosphere (by diffusive gradients in thin-films, or DGT) was influenced by the root system and soil properties, such as pH (by planar optode) and acid phosphatase activity (by soil zymography). Soil acid phosphatase activity increased under Cd stress. The overall pH at rice rhizosphere decreased. Moreover, a close relationship was found between the spatial distributions of soil labile Mn and Cd at the rhizosphere, with higher Mn being associated with lower Cd lability. This study highlights Mn as a key element in regulating rice Cd uptake and enlightens future Mn-based strategies for addressing Cd pollution in rice paddy soils, especially in karst areas with high geochemical background.

Asunto(s)

RESUMEN

In this study, the effects of manure on the availability of sulfonamide antibiotics (SAs) in soils were explored in situ by the Diffusive gradients in thin films (DGT) technique. Five antibiotics, including sulfadiazine (SDZ), sulfamethoxazole (SMX), sulfamethazine (SMZ), sulfachloropyridazine (SCP), and sulfadimethoxine (SDM), were selected as target compounds. Results showed that the manure application to soil could reduce the antibiotic availability indicated by DGT. DGT measurement (CDGT) showed good correlations with the soil solution concentrations (Cd). Manure application can suppress the fluxes of SAs from the soil to the soil solution. Using the DGT-induced soil/sediment flux model (DIFS), the labile pool size (Kdl), the rate constants (k1, k-1) of adsorption and desorption and response time (Tc) of SAs in soils were obtained. The addition of manure increased extractable fraction, labile pool size (Kdl) and k1 but decreased k-1. Together with the nonlinear relationship between DGT fluxes and the reciprocal of diffusive layer thickness (Δg), these findings suggested that the release of SAs from soil particles into the soil solution is thermodynamically and kinetically limited, and the manure application could enhance this limitation. This study offers insight into antibiotic availability in soils caused by manure application.

Asunto(s)

RESUMEN

Blackwater occurs every winter in reservoirs with Eucalyptus plantations. The complexation reaction between ferric iron (Fe3+) and Eucalyptus leachate tannic acid from logging residues (especially leaves) is the vital cause of water blackness. However, the effect of Eucalyptus leaf leaching on the dynamic of iron in sediments and its contribution to reservoir blackwater remain unclear. In this study, two experiments were conducted to simulate the early decomposition processes of exotic Eucalyptus and native Pinus massoniana leaves in water (LW) and water-sediment (LWS) systems. In LW, high concentrations of tannic acid (>45.25 mg/L) rapidly leached from the Eucalyptus leaves to the water column, exceeding those of Pinus massoniana leaves (<1.80 mg/L). The chrominance increased from 5~10 to 80~140, and the water body finally appeared brown instead of black after the leaching of Eucalyptus leaves. The chrominance positively correlated with tannic acid concentrations (R=0.970, p<0.01), indicating that tannic acid was vital for the water column's brown color. Different in LWS, blackwater initially emerged near the sediment-water interface (SWI) and extended upward to the entire water column as Eucalyptus leaves leached. Dissolved oxygen (DO) and transmission values in the overlying water declined simultaneously (R>0.77, p<0.05) and were finally below 2.29 mg/L and 10%, respectively. During the leaching of Eucalyptus leaves, the DGT-labile Fe2+ in sediments migrated from deep to surface layers, and the diffusive fluxes of Fe2+ at the SWI increased from 12.42~19.93 to 18.98~26.28 mg/(m2·day), suggesting that sediment released abundant Fe3+ into the aerobic overlying water. Fe3+ was exposed to high concentrations of tannic acid at the SWI and immediately generated the black Fe-tannic acid complex. The results indicated that the supplement of dissolved Fe3+ from sediments is a critical factor for the periodic blackwater in the reservoirs with Eucalyptus plantations. Reducing the cultivation of Eucalyptus in the reservoir catchment is one of the effective ways to alleviate the reservoir blackwater.

Asunto(s)

RESUMEN

Reservoirs tend to accumulate phosphorus (P) originating from agriculture, industry, and other upstream sources in sediment, with this stored P later released. However, the spatiotemporal dynamics of sediment P release in reservoirs remains unclear. This study investigated the spatiotemporal dynamics in P of the sediment and water of three cascade reservoirs in the Weiyuan River (Tuojiang tributary). The results showed elevated P in sediment [total P (TP): 1208.93 mg kg-1] and water (TP: 0.23 mg L-1) during the low-water season (LWS), which could be attributed to notably higher organic matter content (9.65%), finer particle size (20.95 µm), and extended hydraulic retention time (HRT: 13.13 days) downstream of the cascade reservoirs. Further study employing static in-situ diffusive gradient in thin films (DGT) and dynamic ex-situ adsorption kinetic experiments confirmed that the downstream release of P from sediments [diffusion flux (Fd): 1.67 mg m-2 d-1, equilibrium P concentrations (EPC0): 0.22 ± 0.10 mg L-1] greatly exceeded those upstream (-0.66 ± 0.17 mg m-2 d-1, 0.07 ± 0.001 mg L-1), Fe (II) was a critical factor in regulating sedimentary P release. The combined effects of high P in overlying water and sediment significantly stimulated downstream phytoplankton growth, particularly among cyanobacteria (26.48%) and green algae (8.33%). Further regulatory steps are needed to regulate LWS algal blooms downstream of cascade reservoirs.

RESUMEN

Recycling of phosphorus (P) from waste streams in agriculture is essential to reduce the negative environmental effects of surplus P and the unsustainable mining of geological P resources. Sewage sludge (SS) is an important P source; however, several issues are associated with the handling and application of SS in agriculture. Thus, post-treatments such as pyrolysis of SS into biochar (BC) could address some of these issues. Here we elucidate how patches of SS in soil interact with the living roots of wheat and affect important P-related rhizosphere processes compared to their BC counterparts. Wheat plants were grown in rhizoboxes with sandy loam soil, and 1 cm Ø patches with either SS or BC placed 10 cm below the seed. A negative control (CK) was included. Planar optode pH sensors were used to visualize spatiotemporal pH changes during 40 days of plant growth, diffusive gradients in thin films (DGT) were applied to map labile P, and zymography was used to visualize the spatial distribution of acid (ACP) and alkaline (ALP) phosphatase activity. In addition, bulk soil measurements of available P, pH, and ACP activity were conducted. Finally, the relative abundance of bacterial P-cycling genes (phoD, phoX, phnK) was determined in the patch area rhizosphere. Labile P was only observed in the area of the SS patches, and SS further triggered root proliferation and increased the activity of ACP and ALP in interaction with the roots. In contrast, BC seemed to be inert, had no visible effect on root growth, and even reduced ACP and ALP activity in the patch area. Furthermore, there was a lower relative abundance of phoD and phnK genes in the BC rhizosphere compared to the CK. Hence, optimization of BC properties is needed to increase the short-term efficiency of BC from SS as a P fertilizer.

Asunto(s)

RESUMEN

Pharmaceutical and personal care products (PPCPs) are an important group of emerging contaminants that may threaten organisms at trace concentrations. However, research on the occurrence of PPCPs in urban lakes in China is still scarce. In this study, 15 PPCPs in the Tangxun Lake and the Donghu Lake were collected using the diffusive gradients in thin-films (DGT) technique and analyzed by high performance liquid chromatography tandem-mass spectrometry (HPLC-MS/MS). Thirteen of the 15 targeted PPCPs were detected in the Tangxun Lake, and all PPCPs were detected in the Donghu Lake, with total concentrations ranging from 160 to 730 ng/L (average: 401 ng/L) and 187 to 1933 ng/L (average: 653 ng/L), respectively. Bisphenol A (BPA) was the dominant PPCP, followed by disinfectants in both lakes. The total concentrations of PPCPs in the Donghu Lake were higher than those in the Tangxun Lake. The spatial distribution characteristics of PPCPs in the two lakes were different, with higher total concentrations in the eastern part than in the western part of the Tangxun Lake spatially and higher in the north-western part than in the south-eastern part of the Donghu Lake. The results of the risk assessment showed that BPA and estrone posed high risks to the aquatic environment (RQ ≥ 1), while triclosan and estriol presented a medium risk (0.1 ≤ RQ < 1) in some sites. This study was the first attempt to apply DGT for providing vital data on the evaluation of the ecological risk of PPCPs in the two largest lakes in China, and attention should be paid to the long-term ecological effects caused by the occurrence of PPCPs in lakes.

Asunto(s)

RESUMEN

4-Methylbenzylidene camphor (4-MBC), a typical organic UV filter (OUVF) in personal care products, is considered to be a potential endocrine disruptor due to its estrogenic activity and bioaccumulation. Although 4-MBC residues have been extensively identified in aquatic waters, little is known about their occurrence, levels, and potential risk in coastal waters. This study developed a reliable sampling approach, based on diffusive gradients in thin films (DGT) with XAD-2 as the binding agent, for monitoring 4-MBC in coastal waters. The diffusion coefficients of 4-MBC in freshwater and artificial seawater were 3.65 × 10-6 cm2/s and 3.83 × 10-6 cm2/s, respectively. XAD-2 binding gel showed rapid adsorption to 4-MBC. The accumulated masses of 4-MBC in XAD-2 DGT increased linearly with deployed time for 7 days in freshwater and seawater, which agreed well with theoretical predictions. The sampling performance was independent of ionic strength (0.0001-0.5 M), pH (4.0-8.5), and dissolved organic matter (0-20 mg/L). Field deployment in the river estuary and bathing beach showed that DGT-measured 4-MBC concentrations were consistent in comparison with grab sampling. Environmental risk assessment showed that 4-MBC may pose a medium risk to aquatic organisms based on computed risk quotient (RQ) values. Sewage discharge is the main source of 4-MBC risk, while the residue in recreation beaches contributes more significantly in summer. The established DGT sampling is suitable for seasonal monitoring, source identification, and risk assessment of 4-MBC in coastal waters.

Asunto(s)

RESUMEN

Speciation of thallium (Tl) controls its fate and biogeochemical behaviors. Thus, a sensitive and accurately approach for Tl monitoring is of great demand due to its ultra-low concentration and sensitivity to redox change. In this study, diffusive gradients in thin-films technique (DGT) assembled with novel titanium peroxide (TP) binding gels (TP-DGT) was developed for in situ measurement of dissolved Tl(I) and Tl(III) in waters and sediments. Laboratory test showed a linear mass accumulation of Tl(I) and Tl(III) on the TP binding gels with the deployment time from 4 to 72 h. A fascinating performance of this novel DGT was achieved in a pH range of 4-9, ionic strength range of 0.1-200 mmol L-1, and humic acid concentration of 0-30 mg L-1 with a low detection limit of 0.3 ng L-1 for Tl(I) and 0.6 ng L-1 for Tl(III). The TP binding gels own excellent stability (1-365 d) and high capacity (73.5 µg Tl disc-1) which are suitable for long-term monitoring. Field application in a river indicated that TP-DGT could work effectively, comparable to the grab sampling in waters. For the first time, the TP-DGT coupled with oxygen optode was successfully applied to map 2D distribution patterns of Tl and oxygen simultaneously in the rhizosphere of M. verticillatum L. This study confirms TP-DGT is a promising tool for routine monitoring of Tl in waters and for investigating biogeochemical processes of Tl in sediments.

RESUMEN

The physicochemical exchange dynamics between the solid and solution phases of per- and polyfluoroalkyl substances (PFAS) in soils needs to be better understood. This study employed an in situ tool, diffusive gradients in thin films (DGT), to understand the distribution and exchange kinetics of five typical PFAS in four soils. Results show a nonlinear relationship between the PFAS masses in DGT and time, implying that PFAS were partially supplied by the solid phase in all of the soils. A dynamic model DGT-induced fluxes in soils/sediments (DIFS) was used to interpret the results and derive the distribution coefficients for the labile fraction (Kdl), response time (tc), and adsorption/desorption rates (k1 and k-1). The larger labile pool size (indicated by Kdl) for the longer chain PFAS implies their higher potential availability. The shorter chain PFAS tend to have a larger tc and relatively smaller k-1, implying that the release of these PFAS in soils might be kinetically limited but not for more hydrophobic compounds, such as perfluorooctanesulfonic acid (PFOS), although soil properties might play an important role. Kdl ultimately controls the PFAS availability in soils, while the PFAS release from soils might be kinetically constrained (which may also hold for biota uptake), particularly for more hydrophilic PFAS.

Asunto(s)

RESUMEN

Tungsten (W)-based shots are considered more environmentally safe than lead (Pb)-based shots, but knowledge about the W-shot fate in the soil environment is still limited, especially in terms of minor constituents such as iron, copper, and nickel (Ni). Contaminant behaviour in soil strongly depends on pH; in turn, the corrosion of metal composites may affect the pH locally. The aim of this study was to compare Pb- and W-shot weathering dynamics in soil (silt loam, pH 6.3) and reveal the interplay of shot weathering-induced pH-changes on the mobility of elements using in situ chemical imaging (Diffusive gradients in thin films for labile elements, planar optodes for soil pH) and batch incubation experiments over time (16 months). Despite our expectation to find acidification due to W oxidation, we observed a pH increase by 0.2 units in extracted soil solutions and by 0.6 units in the soil around W-shots as Ni dissolved from the binder phase of the shot. After 10 weeks, release of labile Ni was 3-times higher compared to W despite the low Ni content in the shot (7 %, m/m). Pb-shot oxidation increased soil solution pH by 0.5 units which likely supported mobility of Pb-shot-derived antimony (Sb). Steep gradients of labile W and Pb and soil solution concentrations <0.8 µmol L-1 indicated that transfer from shot to soil was low. Contrastingly, labile Ni and Sb were found up to ~4 mm from the shot surface and in higher soil solution concentrations as suggested by the shot constitution, indicating higher mobility of minor as compared to major shot constituents. After 16 months, 36 % of total Ni were dissolved in the soil solution highlighting the environmental relevance of minor shot constituents in Pb-shot alternatives after short term weathering in soil.

RESUMEN

The extremely serious urban runoff eutrophication and black odorous phenomenon pose a significant threat to the lake aquatic ecosystem, resulting in a significantly increased frequency, magnitude, and duration of algal blooms in lakes. However, few investigations focus on small tributaries of the lakes, despite the ubiquity and potential local importance of these runoffs. Thus, the labile sediments NH4+-N, NO3--N, PO43-, Fe2+, and S2- in black odorous runoff at Wuxi were overall analyzed at high resolution using diffusive gradients in thin films (DGT). The variations in labile N, P, Fe, and S distribution profiles at different sampling sites indicated high heterogeneity in sediments. The concentrations of labile P, Fe, and S showed synchronous variation from the sediment-water interface (SWI) up to -20 mm along sediment profiles. Moreover, there existed a significant positive correlation among labile P, Fe, and S concentrations (p < 0.05), which might represent typical odor compounds' FeS and H2S synchronous release process in urban runoff. Furthermore, the apparent diffusion fluxes of labile P, Fe, and S across the SWI were all released upward, while fluxes of NH4+-N and NO3--N release downward, indicating the sediments act as source and sink of P and N, respectively. Sediments' potential for endogenous P and N fractions release results in the black-odorous water, and sediment finally abouchement the Taihu, which intensifies further lake eutrophication phenomenon.

Asunto(s)

RESUMEN

Chromium (Cr) is a widespread pollutant with high toxicity and mobility. However, the diffusion-resupply kinetics of Cr(VI) between the solid phase and solution in the soils remain unclear. Here, we quantified the contributions of the soil solution and solid phase to the diffusion-resupply process of Cr(VI) in the contaminated soils using the diffusive gradients in thin-films (DGT) and DGT-induced fluxes in soils model. Based on the solution extraction result, Cr(VI) was the main available Cr species in the contaminated soils. Comparing the two diffusion-resupply stages of the kinetic process, the potential hazards due to the resupply from the solid phase can reach 10.71-50.66 %, although the soil solution accounted for the largest proportion of the effective concentration of Cr(VI) (49.34-89.29 %), which was ignored in the traditional equilibrium method. The kinetic parameters can be used to interpret the dynamic process. The resupply ability of the solid phase was closely related to the response time (Tc). The longer Tc was consistent with the low desorption constant, indicating a kinetic limitation. The magnitude of the resupply from the solid phase was related to labile pool size of Cr(VI) and soil organic carbon content. This study established a new quantification method for assessing diffusion-resupply kinetics of Cr(VI) in the soil， indicating the underestimation of Cr(VI) risk based on the use of traditional equilibrium methods. Our data provided a scientific basis for ecological risk assessment, pollution prevention, surface- and groundwater control, and environmental governance in areas with Cr contaminated soil.

Asunto(s)

RESUMEN

Pharmaceutical contaminants in surface water have raised significant concerns because of their potential ecological risks. In particular, coronavirus disease 2019 (COVID-19)-related pharmaceuticals can be released to surface water and reduce environmental water quality. Therefore, reliable and robust sampling tools are required for monitoring pharmaceuticals. In this study, passive sampling devices of diffusive gradients in thin films (DGTs) were developed for sampling 35 pharmaceuticals in surface waters. The results demonstrated that hydrophilic-lipophilic balance (HLB) was more suitable for DGT-based devices compared with XAD18 and XDA1 resins. For most pharmaceuticals, the performance of the HLB-DGT devices were independent of pH (5.0-9.0), ionic strength (0.001-0.5 M), and flow velocity (0-400 rpm). The HLB-DGT devices exhibited linear pharmaceutical accumulation for 7 days, and time-weighted average concentrations provided by the HLB-DGT were comparable to those measured by conventional grab sampling. Compared to previous studies, we extended DGT monitoring to include three antiviral drugs used for COVID-19 treatment, which may inspire further exploration on identifying the effects of COVID-19 on ecological and human health.

Asunto(s)

RESUMEN

Benzophenone(BP)-type UV filters are continuously released into various aquatic environments via the effluent discharge of wastewater treatment plants (WWTPs) and recreational activities in coastal beaches. In this study, we developed a robust and reliable sampling approach, diffusive gradients in thin-films (DGT), for seasonal monitoring of six BP derivatives in coastal waters to investigate their occurrence and environmental risk. The binding capacities of both XAD-2 and HLB gels for test BPs were over 252 µg with no significant deterioration in marine environment, suggesting that theoretically, DGT is capable of sampling for at least 3 months effectively. The diffusion coefficients of BPs in freshwater and seawater were determined for the first time. The sampling performance showed no dependence on environmental conditions including pH (4.0-8.5), ionic strength (0.0001-0.5 M) and dissolved organic matter (0-20 mg L-1). The developed DGT samplers were successfully applied in a river estuary linked to a WWTP and a bathing beach at different periods of one year. Results showed that the concentrations of BPs in the coastal waters were dependent on seasonal variation. The highest level in summer and the ecological risk should be considered based on the risk quotient values. These results demonstrated that the present DGT method is suitable for measuring, characterization, and risk assessment of BPs in freshwater and marine environment.

Asunto(s)