Microplastic polystyrene foam has been found widely in the environment and is readily transported by wind or water. Beached and virgin foams of size 0.45–1 mm were prepared as sorbents to study oxytetracycline sorption. Enhanced adsorption were found in the beached foams compared to the virgin foams, corresponding to the higher specific surface area, micropore area and the degree of oxidation of the former. The Freundlich Kf value was 894 ± 84 ((mg kg⁻¹) (mg L⁻¹)¹/ⁿ) for oxytetracycline adsorption on the beached foams, approximately twice as high as on the virgin foams. Effects of solution pH on adsorption to the beached foams were more pronounced to the virgin foams. Maximum adsorption occurred at pH 5 at which electrostatic repulsion between the microplastic surface and the oxytetracycline zwitterion was minimal, indicating that electrostatic interaction may have regulated adsorption. Moreover, H-bonding and multivalent cationic bridging mechanisms may also have affected the adsorption of oxytetracycline to the beached foams as reflected by the ionic effects. Adsorption was promoted more in the presence of humic acid than of fulvic acid, perhaps owing to π-π conjugation between the humic acid and the microplastic surface which led to enhanced electrostatic attraction for oxytetracycline. This study suggests that weathered polystyrene foams may act as carriers of antibiotics in the environment and their potential risks to ecosystem and human health merit further investigation.

This study systematically explored the effect of humic acid (HA) (as model of natural organic matter) on the kinetics, products and transformation pathway of triclosan (TCS) by laccase-catalyzed oxidation. It was found that TCS could be effectively transformed by laccase-catalysis, with the apparent second-order rate constant being 0.056 U⁻¹ mL min⁻¹. HA inhibited the removal rate of TCS. HA-induced inhibition was negatively correlated with HA concentration in the range of 0–10 mg L⁻¹ and pH-dependent from 3.5 to 9.5. FT-IR and ¹³C NMR spectra showed a decrease of aromatic hydroxyl (phenolic) groups and an increase of aromatic ether groups, indicating the cross-linking of HA via C-O-C and C-N-C bonds during enzyme-catalyzed oxidation. Ten principle oxidative products, including two quinone-like products (2-chlorohydroquinone, 2-chloro-5-(2,4-dichlodichlorophenoxy)-(1,4)benzoquinone), one chlorinated phenol (2,4-dichlorophenol (2,4-DCP)), three dimers, two trimmers and two tetramers, were detected by gas chromatograghy/mass spectrometry (GC-MS) and high performance liquid chromatography/quadrupole time-of-flight/mass spectrometry (HPLC/Q-TOF/MS). The presence of HA induced significantly lesser generation of self-polymers and enhanced cross-coupling between HA and self-polymers via C-O-C, C-N-C and C-C coupling pathways. A plausible transformation pathway was proposed as follows: TCS was initially oxidized to form reactive phenoxyl radicals, which self-coupled to each other subsequently by C-C and C-O pathway, yielding self-polymers. In addition, the scission of ether bond was also observed. The presence of HA can promote scission of ether bond and further oxidation of phenoxyl radicals, forming hydroxylated or quinone-like TCS. This study shed light on the behavior of TCS in natural environment and engineered processes, as well provided a perspective for the water/wastewater treatment using enzyme-catalyzed oxidation techniques.

Gasoline vehicles are a major source of anthropogenic secondary organic aerosols (SOAs). However, current models based on known precursors fail to explain the substantial SOAs from vehicle emissions due to the inadequate understanding of the formation mechanism. To provide more information on this issue, the formation of SOAs from ozonolysis of four light-duty gasoline vehicle exhaust systems was investigated with a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS). Remarkable SOAs formation was observed and the SOAs were primarily aliphatic alkenes. PI mass spectra of the SOAs from all vehicles exhibited similar spectral patterns (a regular mass group with m/z at 98, 112, 126 …). Interestingly, most carbonyl products of aliphatic alkenes observed as major gaseous products have specific molecular weights, and the main formation pathway of SOAs can be explained well using aldol condensation reactions of these carbonyls. This is a direct observation of the aldol condensation as a dominated pathway for SOAs formation, and the first report on the composition and formation mechanism of the SOAs from the ozonolysis of gasoline vehicle exhaust is given. The study reveals that low molecular weight alkenes may play a more significant role in vehicle-induced SOAs formation than previously believed. More importantly, the PI mass spectra of SOAs from vehicles show similarities to the field aerosol sample mass spectra, suggesting the possible significance of the aldol condensation reactions in ambient aerosol formation. Since carbonyls are a major degradation product of biogenic and anthropogenic VOCs through atmospheric oxidation processes, the mechanism proposed in this study can be applied more generally to explain aerosol formation from the oxidation of atmospheric hydrocarbons.

In Mediterranean areas, dry deposition is a major component of the total atmospheric N input to natural habitats, particularly to forest ecosystems. An innovative approach, combining the empirical inferential method (EIM) for surface deposition of NO₃⁻ and NH₄⁺ with stomatal uptake of NH₃, HNO₃ and NO₂ derived from the DO₃SE (Deposition of Ozone and Stomatal Exchange) model, was used to estimate total dry deposition of inorganic N air pollutants in four holm oak forests under Mediterranean conditions in Spain. The estimated total deposition varied among the sites and matched the geographical patterns previously found in model estimates: higher deposition was determined at the northern site (28.9 kg N ha⁻¹ year⁻¹) and at the northeastern sites (17.8 and 12.5 kg N ha⁻¹ year⁻¹) than at the central-Spain site (9.4 kg N ha⁻¹ year⁻¹). On average, the estimated dry deposition of atmospheric N represented 77% ± 2% of the total deposition of N, of which surface deposition of gaseous and particulate atmospheric N averaged 10.0 ± 2.9 kg N ha⁻¹ year⁻¹ for the four sites (58% of the total deposition), and stomatal deposition of N gases averaged 3.3 ± 0.8 kg N ha⁻¹ year⁻¹ (19% of the total deposition). Deposition of atmospheric inorganic N was dominated by the surface deposition of oxidized N in all the forests (means of 54% and 42% of the dry and total deposition, respectively). The relative contribution of NO₂ to dry deposition averaged from 19% in the peri-urban forests to 11% in the most natural site. During the monitoring period, the empirical critical loads provisionally proposed for ecosystem protection (10–20 kg N ha⁻¹ year⁻¹) was exceeded in three of the four studied forests.

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.

In this study, we examined the removal of arsenite (As(III)) and arsenate (As(V)) by perilla leaf-derived biochars produced at 300 and 700 °C (referred as BC300 and BC700) in aqueous environments. Results revealed that the Langmuir isotherm model provided the best fit for As(III) and As(V) sorption, with the sorption affinity following the order: BC700-As(III) > BC700-As(V) > BC300-As(III) > BC300-As(V) (QL = 3.85–11.01 mg g⁻¹). In general, As removal decreased (76–60%) with increasing pH from 7 to 10 except for the BC700-As(III) system, where notably higher As removal (88–90%) occurred at pH from 7 to 9. Surface functional moieties contributed to As sequestration by the biochars examined here. However, significantly higher surface area and aromaticity of BC700 favored a greater As removal compared to BC300, suggesting that surface complexation/precipitation dominated As removal by BC700. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy demonstrated that up to 64% of the added As(V) was reduced to As(III) in BC700- and BC300-As(V) sorption experiments, and in As(III) sorption experiments, partial oxidation of As(III) to As(V) occurred (37–39%). However, XANES spectroscopy was limited to precisely quantify As binding with sulfur species as As2S3-like phase. Both biochars efficiently removed As from natural As-contaminated groundwater (As: 23–190 μg L⁻¹; n = 12) despite in the presence of co-occurring anions (e.g., CO3²⁻, PO4³⁻, SO4²⁻) with the highest levels of As removal observed for BC700 (97–100%). Overall, this study highlights that perilla leaf biochars, notably BC700, possessed the greatest ability to remove As from solution and groundwater (drinking water). Significantly, the integrated spectroscopic techniques advanced our understanding to examine complex redox transformation of As(III)/As(V) with biochar, which are crucial to determine fate of As on biochar in aquatic environments.

Mercury (Hg) has a complex atmospheric transformation cycle and acts as a global pollutant. Size-specific particle bound mercury (PBM) was implemented in different functional (industrial, urban and suburban) areas in Shanghai, China. The total concentration of 13-staged PBM (rang of 0.01–18.0 μm) varied of 99.0–611 pg/m3, with an average value of 318 ± 144 pg/m3. The Gaoqiao petrochemical industry (GQPI) site showed the highest concentrations, whereas the suburban Shanghai Jiao Tong University (SJTU) displayed the lowest. The PBM in nucleation, accumulation and coarse modes were 7.63–96.7, 69.5–455, and 9.43–176 pg/m3, respectively, and the fractions of 0.56–1.00 and 0.32–0.56 μm were the two most abundant. Both OC and EC displayed unimodal distribution patterns (peak of 0.56–1.00 μm) at GQPI, while bimodal distributions were observed at urban and suburban sites. Statistically positive correlations between the overall PBM and the corresponding PM and carbonaceous compounds (r = 0.38–0.54, p < 0.01), indicating their similar origins and OC/EC enhanced gaseous mercury forming PBM. The gas–particle partition model predicted gaseous oxidized mercury (GOM) were 253 ± 133, 237 ± 122, and 257 ± 144 pg/m3 for GQPI, SAES and SJTU, respectively. The particle proportions of divalent mercury in the fraction of 0.32–1.00 μm were substantial (>80%), but smaller (<50%) for nucleation and coarse modes. The fraction of 9.90–18.00 μm occupied nearly 50% of the overall dry deposition fluxes of mercury. These finding highlight the emissions from different mercury and OC/EC origins, caused different size-specific distributions of PBM, which further affect their gas-particle partitioning and dry deposition of mercury species.

Gaseous elemental mercury (Hg0) is a prolific and persistent contaminant in the atmosphere. Atmospheric concentrations of Hg0 were determined from 17 September to 7 October 2015 in the northwest Sea of Japan aboard the Russian research vessel Professor Gagarinsky. Simultaneous measurements of Hg0 concentrations were performed 2 m and 20 m above the sea surface using automatic Hg0 analysers RA-915M and RA-915+, respectively. Concentrations ranged from 0.3 to 25.9 ng/m3 (n = 5207) and from 0.3 to 27.8 ng/m3 (n = 4415), with medians of 1.7 and 1.6 ng/m3, respectively. Elevated Hg0 was observed during three episodes from 19 to 22 September, likely caused by one or more of the following factors: 1) atmospheric transport of Hg0 from the west and south-west (from N. Korea, China, and the Yellow Sea region); 2) Hg0 emission from the sea due to pollution by water from the Tumannaya River; or 3) underwater geological activities. Increased Hg0 concentration was observed during periods when air masses flowed from the south, and low concentrations were observed when air masses came from the north. A daytime increase of Hg0 concentrations at a height of 2 m occurred simultaneously with decreasing Hg0 at a height of 20 m. These diurnal variations suggest that two contrasting processes occur during the daytime in the marine boundary layer (MBL): Hg0 emission from the sea surface and Hg0 oxidation in the MBL by active halogens formed by photolysis.

In this study, a novel biochar-supported zero valent iron (BC-nZVI) was synthesized through a green method. A high performance on the simultaneous removal of Cu²⁺ and bisphenol A (BPA) by a combination of BC-nZVI with persulfate (BC-nZVI/PS) system was successfully achieved. The simultaneous efficiencies of Cu²⁺ and BPA could reach 96 and 98% within 60 min, respectively. Both HO• and SO₄•⁻ were two major reactive species in BC-nZVI/PS system, and SO₄•⁻ was primary radical responsible for the degradation of BPA. Four kinds of Cu species, such as Cu(OH)₂, CuO, Cu₂O and Cu⁰ were generated via the adsorption and reduction of the BC-nZVI, whereas six kinds of products of BPA including p-isopropenyl phenol and 4-isopropylphenol were generated via the combined oxidation of SO₄•⁻ and HO•. The possible reaction mechanism for the simultaneous removal of Cu²⁺ and BPA by BC-nZVI/PS system contained a synergistic effect between the reduction of Cu²⁺ and the oxidation of BPA. This is the first report on the feasibility of the remediation of coexistence of heavy metal and organic compound in aquatic environment using the BC-nZVI/PS system.

Two hundred sixty-three fine particulate matter (PM2.5) samples collected on 3-day intervals over a 14-month period at two sites in the San Joaquin Valley (SJV) were analyzed for organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), and organic molecular markers. A unique source profile library was applied to a chemical mass balance (CMB) source apportionment model to develop monthly and seasonally averaged source apportionment results. Five major OC sources were identified: mobile sources, biomass burning, meat smoke, vegetative detritus, and secondary organic carbon (SOC), as inferred from OC not apportioned by CMB. The SOC factor was the largest source contributor at Fresno and Bakersfield, contributing 44% and 51% of PM mass, respectively. Biomass burning was the only source with a statistically different average mass contribution (95% CI) between the two sites. Wintertime peaks of biomass burning, meat smoke, and total OC were observed at both sites, with SOC peaking during the summer months. Exceptionally strong seasonal variation in apportioned meat smoke mass could potentially be explained by oxidation of cholesterol between source and receptor and trends in wind transport outlined in a Residence Time Analysis (RTA). Fast moving nighttime winds prevalent during warmer months caused local emissions to be replaced by air mass transported from the San Francisco Bay Area, consisting of mostly diluted, oxidized concentrations of molecular markers. Good agreement was observed between SOC derived from the CMB model and from non-biomass burning WSOC mass, suggesting the CMB model is sufficiently accurate to assist in policy development. In general, uncertainty in monthly mass values derived from daily CMB apportionments were lower than that of CMB results produced with monthly marker composites, further validating daily sampling methodologies.Strong seasonal trends were observed for biomass and meat smoke OC apportionment, and monthly mass averages had lowest uncertainty when derived from daily CMB apportionments.