International audience | Accumulation of copper (Cu) in soils due to the application of fungicides may be toxic for organisms and hence affect winegrowing sustainability. Soil parameters such as pH and dissolved organic matter (DOM) are known to affect the availability of Cu. In this study, we investigated the contribution of chromophoric and fluorescent DOM properties to the prediction of Cu availability in 18 organic vineyard soils in the Bordeaux winegrowing area (France). The DOM parameters, assessed through absorbance and fluorescence analyses, and proxies for Cu availability (total soluble Cu and free ionic Cu2+) were measured in 0.01 M KCl extracts. Total soluble Cu (CuKCl) varied 23-fold while free ionic Cu2+ varied by a factor of 4600 among the soils. DOC concentrations were similar among the soils, but the samples differed in the quality of DOM as assessed by optical spectroscopy. Multilinear regression models with and without DOM quality parameters were investigated to predict Cu availability. The best model for CuKCl successfully explained 83% of variance and included pH, CuT, and two DOM fluorescence quality indices, the FI fluorescence index, which distinguishes between microbial and higher plant origins, and the HIX humification index. For the prediction of Cu2+, pH alone explained 88% of variance and adding DOM parameters did not improve modelling. The two Cu availability proxies were related to pH. This study confirms the prominent role of pH in Cu availability and underlines the importance of DOM quality to better predict Cu solubility

Carbonaceous constituents have various adverse impacts on human health, visibility, and climate change. Although comprehensive studies on the characteristics of carbonaceous constituents have been conducted recently, systematic studies covering both the mass characteristics and light-absorption properties of carbonaceous constituents on a regional scale in China are quite limited. In this study, current seasonal measurements of organic carbon (OC) and elemental carbon (EC) in PM₂.₅ were investigated during autumn and winter (1–30 October 2017 and December 18, 2017 to January 17, 2018) in six selected cities located at the eastern foot of the Taihang Mountains: Beijing, Baoding, Shijiazhuang, Handan, Xinxiang, and Zhengzhou. Seasonal variations were similar when Beijing was excluded. The lowest concentrations of OC (18.33 ± 9.39 μg/m³) and EC (7.66 ± 5.64 μg/m³) were observed in Xinxiang (autumn) and Beijing (winter), respectively, while the highest concentrations of OC (38.43 ± 62.10 μg/m³) and EC (12.24 ± 24.67 μg/m³) occurred in Baoding during winter mainly due to elevated fuel combustion for space heating. The results of the potential source contribution function (PSCF) analysis suggested that border zones between several provinces in North China should be highlighted in order to strengthen pollution control. Moreover, by separating the optical properties of brown carbon from those of black carbon, we were able to estimate the contributions of brown carbon to the PM₂.₅ total light-absorption coefficient. The results show that the brown carbon absorption coefficient (at 405 nm) in winter at six sites accounted for 21.2%, 33.3%, 34.7%, 39.1%, 48.6%, and 23.3% of the PM₂.₅ light absorption, which are values that are comparable to the contribution of black carbon in Xinxiang. These results provide a more comprehensive understanding of carbonaceous constituents on a regional scale.

As an emerging brominated flame retardant (BFR), tetrabromobisphenol S (TBBPS) has been frequently detected in the environmental media and organisms. Knowledges on the transformation and fate of TBBPS in both environment and engineering systems are essential to its ecological risk assessment. Herein, we reported the photochemical decomposition of TBBPS in aqueous solution upon 254 nm ultraviolet irradiation (UV₂₅₄). Results show that TBBPS was highly photoreactive, most likely due to the presence of four ortho-bromine substituents. The molar absorption coefficient and quantum yield of TBBPS were found to be pH-dependent, with the monoanionic form being most photoreactive. A series of photoproducts were identified by solid phase extraction (SPE) combined with liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI(+)-MS/MS. The photolysis of TBBPS likely proceeded through photonucleophilic substitution, photoreductive debromination, and β-scission reactions. A ketocarbene, possibly derived from the lower lying excited triplet state, was proposed to be involved in the photolysis of TBBPS. Ion chromatography analysis revealed that debromination occurred quickly, and the yield of bromide (Br⁻) approached 100% after 90 min irradiation. The presence of SRNOM and MRNOM inhibited the photodegradation rate of TBBPS, which is likely due to the light-screening and physical quenching effects of natural organic matter (NOM). Our results reveal that photolysis is an important process for the attenuation of TBBPS in aquatic system; however, naturally occurring species such as NOM can appreciably retard the decay of TBBPS.

Chromophoric dissolved organic matter (CDOM) in rivers is mainly affected by natural conditions and human activities and can reflect the watershed pollution status to a certain extent. The Yellow River is one of the largest contributors to the global riverine sediment flux from the land to ocean, and there is a paucity of information on how the optical properties of CDOM have the potential to serve as an indicator of water quality for the sediment-laden Yellow River. In this study, a three-dimensional fluorescence parallel factor (PARAFAC) analysis method was applied to investigate the seasonal and spatial variations in CDOM fluorescence components and spectral characteristics from the source region to the estuary in the mainstream of Yellow River. The relationships of CDOM with water quality indicators and trophic state were also analyzed. Six PARAFAC components (C1–C6) were identified and grouped into two categories: humic-like components (C1–C4), which accounted for 85.8 %, and protein-like components (C5 and C6), which accounted for only 14.2 %. The CDOM components, spectral parameters, and their clear correlations with the main ions (Na⁺ and Cl⁻) all indicated that the humic-like components may be primarily derived from nonpoint source erosion, and the protein-like components were mainly derived from point source discharges in the watershed. The combination of the CDOM absorption coefficient at 254 nm (a(254)), spectral slope ratio (SR), specific UV absorbance SUVA₂₅₄, and fluorescence index (FI) had a good predictive ability for the key water quality indicators (total nitrogen (TN), dissolved total nitrogen (DTN), total phosphorus (TP), dissolved total phosphorus (DTP), and chlorophyll a (Chl a)) and trophic state index (TSI). Therefore, some fluorophores and UV spectral parameters of CDOM in the Yellow River can be used for rapid water quality monitoring and pollution source indication, especially pollutants related to nitrogen and phosphorus nutrients in the basin.

To prevent spreads of Coronavirus disease-2019 (COVID-19), China adopted the lockdown measures in late January 2020, providing a platform to study the response of air quality and atmospheric chemical and physical properties to strict reduced emissions. In this study, the continuous measurements of aerosol light absorption were conducted in Nanjing, east China, from January 3 to March 31, 2020. Our results showed that the contribution of black carbon (BC) to light absorption at the different wavelengths was more than 75% and the rest light absorption was contributed by brown carbon (BrC), which was mainly originated from primary emissions. Secondary BrC absorption, which was mainly produced by photochemical oxidation, constituted a minor fraction (2–7%) of the total absorption. Compared with the sampling in the pre-lockdown, the significant decreases of BC (43%) and secondary BrC absorption (31%) were found during the lockdown period, resulting in a substantial decrease of solar energy absorbance by 36% on a local scale. The control measures also changed the diurnal variations of light absorption. Due to the reduced emissions, the relative fraction of fossil fuel to BC also dropped from 78% in the pre-lockdown to 71% in the lockdown. The concentrations of BC, PM₂.₅ and NO₂ decreased 1.1 μg m⁻³, 33 μg m⁻³ and 9.1 ppb whereas O₃ concentration increased 9.0 ppb during the COVID-19 lockdown period. The decreased concentrations of BC, PM₂.₅ and NO₂ were mainly contributed by both emission reduction (51–64%) and meteorological conditions (36–49%). Our results highlighted that the balance of control measures in alleviation of particulate matter (PM) and O₃ pollution, and meteorology should be seriously considered for improvement of air quality in this urban city of China.

The perdurability of plastics in the environment is one of the major concerns of plastic pollution and, as a consequence, oceans are accumulating large amounts of plastic. The degradation of conventional and biobased materials was evaluated through a laboratory experiment for a year simulating four different conditions in the marine environment. The water column environmental compartment was simulated under euphotic and aphotic (with and without light availability) conditions. The seafloor environmental compartment was simulated with sediment under non-polluted and polluted conditions. By combining weight loss (%), spectroscopic and thermal analyses, the degradation patterns regarding the polymer structure were assessed. The studied biobased materials were polylactic acid (PLA) based materials and showed higher degradability than conventional ones. The weight loss of conventional materials was not influenced by the water column or sediment, while in PLA-based materials, the degradation rates were ca. 5 times greater in the sediment than in the water column. The absorbance (Abs) value at 3400 cm⁻¹ for polyethylene terephthalate (PET), and carbonyl (CO) index for PET and PLA could be useful to detect early signs of degradation. The crystallization index could be a useful parameter to discriminate degradation stages. The obtained results highlight the different degradability rates of materials depending on the specific environmental marine conditions.

The occurrence and distributions of selected endocrine-disrupting chemicals (EDCs), along with related environmental factors, were investigated in two rivers and six reservoirs in the Pearl River Delta. The vertical profiles of aqueous 4-tert-octylphenol (OP), 4-nonylphenol (NP), and estrone (E1) were constant, with little change in concentration between the surface and the river bottom, while higher aqueous concentrations of bisphenol A (BPA) were found in the bottom layers of the rivers. OP and NP in suspended particulate matter (SPM) were transferred from the surface to the bed layer, ultimately accumulating in the sediment. However, the particulate profiles of BPA and E1 both featured increases from the surface to the bottom layers and attenuation in the river bed. Dissolved oxygen (DO), water temperature, and pH were negatively correlated with the EDC concentrations, and negative relationships between DO and distribution coefficient (Kd) values for OP and NP were found as well. This indicated that these environmental parameters were primarily responsible for the EDC vertical distribution and SPM-water partitioning in the rivers. Positive relationships were observed between chlorophyll a and EDCs in the particulate phase, and the algae/water Kd values for EDCs in reservoirs were comparable to the SPM/water and sediment/water Kd values from the rivers. These results suggest that algae played an important role in regulating the distribution of EDCs in surface waters. Moreover, relationships between UV absorbance and EDCs revealed that π-π interactions were among the dissolved organic carbon (DOC)-EDC binding mechanisms and that DOC fractions with higher degrees of aromaticity and humification possessed higher affinities towards EDCs.

The work was conducted to establish contamination from improper disposal of hazardous wastes containing lead (Pb) and antimony (Sb) into nearby soils. Besides other elements in the affected area, the biological role of Sb, its behaviour in the pedosphere and uptake by plants and the food chain was considered. Wastes contained 139532 ± 9601 mg kg−1 (≈14%) Pb and 3645 ± 194 mg kg−1 (≈0.4%) Sb respectively and variability was extremely high at a decimetre scale. Dramatically high concentrations were also found for As, Cd, Cu, Mn, Ni, Sn and Zn. In adjacent natural soils metal(oid)s amounts decreased considerably (Pb 5034 ± 678 mg kg−1, Sb 112 mg kg−1) though largely exceeded the directives for a given soil use. Metal(oid)s potential mobility was assessed by using H2O→KNO3→EDTA sequential extractions, and EDTA extracts showed the highest concentration suggesting stable humus-metal complexes formation. Nevertheless, selected plants showed high absorption potential of the investigated elements. Pb and Sb values for Dittrichia viscosa grown in wastes was 899 ± 627 mg kg−1 and 37 ± 33 mg kg−1 respectively. The same plant showed 154 ± 99 mg kg−1 Pb and 8 ± 4 mg kg−1 Sb in natural soils. Helichrysum stoechas had 323 ± 305 mg kg−1 Pb, and 8 ± 3 mg kg−1 Sb. Vitis vinifera from alongside vineyards contained 129 ± 88 mg kg−1 Pb and 18 ± 9 mg kg−1 Sb, indicating ability for metal uptake and warning on metal diffusion through the food chain. The biological absorption coefficient (BAC) and the translocation factor (TF) assigned phytoextraction potential to Dittrichia viscosa and Foeniculum vulgare and phytostabilization potential to Helichrysum stoechas. Dissolved metal (oid)s in the analysed water strongly exceeded the current directive being a direct threat for livings. Data warned against the high contamination of the affected area in all its compartments. Even though native plants growing in metal-contaminated sites may have phytoremediation potential, high risk of metal diffusion may threat the whole ecosystem.

Extracellular polymeric substances (EPS) from bloom-forming cyanobacteria exist ubiquitously in eutrophic waters, while their effects on the aggregation/stabilization of nanoparticles remain unknown. In this study, the stability of ZnO nanoparticles (ZNPs) upon adsorption of cyanobacterial EPS was investigated by using two dimensional ATR-FTIR correlation spectroscopy, XPS and DLVO theory. Results showed that the adsorption process followed the Langmuir isotherm and pseudo-second-order kinetics both for the total organic contents as well as the individual parallel factor-derived components. The physicochemical and spectroscopic techniques revealed the mechanism of both electrostatic attraction and surface complexation in EPS adsorption. Further analysis showed increased absorbance and turbidity of ZNPs solutions with EPS addition, demonstrating the enhanced colloidal stability. The DLVO theory explained that the increased energy barriers and values of second energy maximum were responsible for the stability enhancement. This study facilitates a deeper insight into the environmental behavior of nanoparticles in eutrophic algae-rich waters.

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THgd), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THgd to DOC (r² = 0.87), but progressively stronger correlations of THgd with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV254 absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THgd relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THgd concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THgd flux in drainage waters. Ultraviolet absorbance measurements are a cost-effective proxy to estimate dissolved mercury concentration in stream water.