Iron and Steel Industry Emissions: A Global Analysis of Trends and Drivers.

The iron and steel industry (ISI) is important for socio-economic progress but emits greenhouse gases and air pollutants detrimental to climate and human health. Understanding its historical emission trends and drivers is crucial for future warming and pollution interventions. Here, we offer an exhaustive analysis of global ISI emissions over the past 60 years, forecasting up to 2050. We evaluate emissions of carbon dioxide and conventional and unconventional air pollutants, including heavy metals and polychlorinated dibenzodioxins and dibenzofurans. Based on this newly established inventory, we dissect the determinants of past emission trends and future trajectories. Results show varied trends for different pollutants. Specifically, PM2.5 emissions decreased consistently during the period 1970 to 2000, attributed to adoption of advanced production technologies. Conversely, NOx and SO2 began declining recently due to stringent controls in major contributors such as China, a trend expected to persist. Currently, end-of-pipe abatement technologies are key to PM2.5 reduction, whereas process modifications are central to CO2 mitigation. Projections suggest that by 2050, developing nations (excluding China) will contribute 52-54% of global ISI PM2.5 emissions, a rise from 29% in 2019. Long-term emission curtailment will necessitate the innovation and widespread adoption of new production and abatement technologies in emerging economies worldwide.

A Novel Punch Technique for Facial Pigmented Melanocytic Nevus.

The punch tool is a swift and practical instrument in the facial pigmented melanocytic nevus. However, few studies have evaluated the efficacy of the method for facial pigmented nevus. The aim of this study was to evaluate the practicability and effectiveness of removing facial pigmented nevus by punch biopsy technique. This was an observational study of patients with facial pigmented nevus in the Hospital of Plastic Surgery, Weifang Medical University. The ages of patients ranged from 15 to 36 years (average, 25 y). The outcome evaluations included Vancouver Scar Scale (VSS) score, esthetic appearance, and patient satisfaction. Following standard procedures, preoperative surgical excision was performed with safety margins. Anatomopathologic analysis of the surgical specimen was used as the gold standard to evaluate the accuracy of diagnosis by punch biopsy. From January 2019 to January 2020, this punch technique was carried out on 96 patients (151 pigmented nevus) with 35 melanocytic nevus on the forehead, 39 on the cheek, 21 on the eyelid, and 45 on the nose, whereas 11 were on nasolabial folds. The diameters of pigmented nevus are 0.5 to 10 mm on the face. All patients were evaluated at a follow-up visit ranging from 6 to 20 months (average, 11±1.5 mo) and healed with no complication. The histopathological examinations of the skin lesions showed benign outcomes. The mean Vancouver Scar Scale were 1.1±0.4. Ideal cosmetic and functional outcomes were achieved in 94 patients (97.9%). All patients achieved complete satisfaction except 2 patients with partial satisfaction. No recurrences and complications were recorded. This study demonstrated that the punch technique is an effective method to remove facial pigmented melanocytic nevus with acceptable functional and esthetic outcomes without relapse.

Spatial Distributions, Compositional Profiles, Potential Sources, and Intfluencing Factors of Microplastics in Soils from Different Agricultural Farmlands in China: A National Perspective.

More attention has been paid to ubiquitous microplastics (MPs). As a major food producer, the situation of MPs in China's farmland is of even greater concern. Spatial distributions, characteristics, and compositions of MPs in five types of agricultural lands with representative crops were investigated by collecting 477 soil samples from 109 cities in 31 administrative regions of mainland China. To better control MPs in farmland, nearly 400 field questionnaires were obtained, and meteorological conditions, soil properties, and other statistics were collected to quantify potential sources and determine influencing factors. The average abundances of MPs was 2462 ± 3767 items/kg in the agricultural soils, and MP abundance in the greenhouses, farmlands with film mulching, and blank farmlands from four integrated physical geographic regions were determined. The contributions of agricultural films, livestock and poultry manures, irrigation water, and air deposition to MPs in farmlands have been calculated. Influencing factors, such as recovery method, plowing frequency, meteorological conditions, and part of soil properties, were significantly correlated with the abundances of MPs in the agricultural soils (p < 0.05), while mulching age mainly affected MPs in the greenhouses (p < 0.05). This study provides basic scientific data for decision-making and further analysis.

Impact of Polymer Colonization on the Fate of Organic Contaminants in Sediment.

Plastic pellets and microbes are important constitutes in sediment, but the significance of microbes colonizing on plastic pellets to the environmental fate and transport of organic contaminants has not been adequately recognized and assessed. To address this issue, low-density polyethylene (LDPE), polyoxymethylene (POM) and polypropylene (PP) slices were preloaded with dichlorodiphenyltrichloroethanes (DDTs), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) and incubated in abiotic and biotic sediment microcosms. Images from scanning electron microscope, Lysogeny Broth agar plates and confocal laser scanning microscope indicated that all polymer slices incubated in biotic sediments were colonized by microorganisms, particularly the LDPE slices. The occurrence of biofilms induced higher dissipation rates of DDTs and PAHs from the LDPE slice surfaces incubated in the biotic sediments than in the abiotic sediments. Plastic colonization on LDPE slice surfaces enhanced the biotransformation of DDT and some PAHs in both marine and river sediments, but had little impact on PCBs. By comparison, PP and POM with unique properties were shown to exert different impacts on the physical and microbial activities as compared to LDPE. These results clearly demonstrated that the significance of polymer surface affiliated microbes to the environmental fate and behavior of organic contaminants should be recognized.

Polycyclic aromatic hydrocarbons in ambient air, surface soil and wheat grain near a large steel-smelting manufacturer in northern China.

The total concentrations and component profiles of polycyclic aromatic hydrocarbons (PAHs) in ambient air, surface soil and wheat grain collected from wheat fields near a large steel-smelting manufacturer in Northern China were determined. Based on the specific isomeric ratios of paired species in ambient air, principle component analysis and multivariate linear regression, the main emission source of local PAHs was identified as a mixture of industrial and domestic coal combustion, biomass burning and traffic exhaust. The total organic carbon (TOC) fraction was considerably correlated with the total and individual PAH concentrations in surface soil. The total concentrations of PAHs in wheat grain were relatively low, with dominant low molecular weight constituents, and the compositional profile was more similar to that in ambient air than in topsoil. Combined with more significant results from partial correlation and linear regression models, the contribution from air PAHs to grain PAHs may be greater than that from soil PAHs.

Kinetics of Brominated Flame Retardant (BFR) Releases from Granules of Waste Plastics.

Plastic components of e-waste contain high levels of brominated flame retardants (BFRs), whose releases cause environmental and human health concerns. This study characterized the release kinetics of polybrominated diphenyl ethers (PBDEs) from millimeter-sized granules processed from the plastic exteriors of two scrap computer displays at environmentally relevant temperatures. The release rate of a substitute of PBDEs, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), from the waste plastics, was reported for the first time. Deca-BDE was the most abundant PBDE congeners in both materials (87-89%), while BTBPE was also present at relatively high contents. The release kinetics of BFRs could be modeled as one-dimensional diffusion, while the temperature dependence of diffusion coefficients was well described by the Arrhenius equation. The diffusion coefficients of BFRs (at 30 °C) in the plastic matrices were estimated to be in the range of 10-27.16 to 10-19.96 m2·s-1, with apparent activation energies between 88.4 and 154.2 kJ·mol-1. The half-lives of BFR releases (i.e., 50% depletion) from the plastic granules ranged from thousands to tens of billions of years at ambient temperatures. These findings suggest that BFRs are released very slowly from the matrices of waste plastics through molecular diffusion, while their emissions can be significantly enhanced with wear-and-tear and pulverization.

Bioaccessibility of PAHs in Fuel Soot Assessed by an in Vitro Digestive Model with Absorptive Sink: Effect of Food Ingestion.

We investigated the effects of changing physiological conditions in the digestive tract expected with food ingestion on the apparent bioaccessibility (Bapp) of 11 polycyclic aromatic hydrocarbons (PAHs) in a fuel soot. A previously established in vitro digestive model was applied that included silicone sheet as a third-phase absorptive sink simulating passive transfer of PAHs to intestinal epithelium in the small intestine stage. The Bapp is defined as the fraction found in the digestive fluid plus sheet after digestion. We determined that Bapp was independent of gastric pH and addition of nonlipid milk representing dietary proteins and carbohydrates, whereas it increased with bile acids concentration (2.0-10 g/L), small intestinal pH (5.00-7.35), and addition of soybean oil representing dietary lipid (100% and 200% of the mean daily ingestion by 2-5 year olds in the U.S.). Bapp of PAHs increases with small intestinal pH due to the combined effects of mass transfer promotion from nonlabile to labile sorbed states in the soot, weaker sorption of the labile state, and increasingly favorable partitioning from the digestive fluid to the silicone sink. Under fed conditions, Bapp increases with inclusion of lipids due to the combined effects of mass transfer promotion from nonlabile to labile states, and increasingly favorable partitioning into bile acid micelles. Our results indicate significant variability in soot PAH bioaccessibility within the range of physiological conditions experienced by humans, and suggest that bioaccessibility will increase with coconsumption of food, especially food with high fat content.

Bioacessibility of PAHs in fuel soot assessed by an in vitro digestive model: effect of including an absorptive sink.

Polycyclic aromatic hydrocarbons (PAHs) associated with soot or black carbon can enter the human digestive tract by unintentional ingestion of soil or other particles. This study investigated the bioaccessibility of 11 PAHs in a composite fuel soot sample using an in vitro digestive model that included silicone sheet as an absorptive sink during the small intestinal digestion stage. The sheet was meant to simulate the passive transfer of PAHs in lumen fluid across the small intestinal epithelium, which was postulated to promote desorption of labile PAHs from the soot by steepening the soot-fluid concentration gradient. We show that the presence of silicone sheet during a 4 h default digestion time significantly increased the apparent bioaccessible fraction (Bapp, %), defined as the sum in the sheet and digestive fluid relative to the total PAH determined. The ability to increase Bapp for most PAHs leveled off above a sheet-to-soot ratio of 2.0 g per 50 mg, indicating that the sheet is an effective absorptive sink and promotes desorption in the mentioned way. Enhancement of Bapp by the sheet correlated positively with the octanol-water partition coefficient (Kow), even though the partition coefficient of PAH between sheet and digestive fluid (which contains bile acid micelles) correlated negatively with Kow. It was hypothesized that PAHs initially in the soot exist in labile and nonlabile states. The fraction of labile PAH still sorbed to the soot residue after digestion, and the maximum possible (limiting) bioaccessibility (Blim) could be estimated by varying the sheet-to-soot ratio. We show conclusively that the increase in bioccessibility due to the presence of the sheet is accounted for by a corresponding decrease in fraction of labile PAH still sorbed to the soot. The Blim ranged from 30.8 to 62.4%, independent of molecular size. The nonlabile fraction of individual PAHs (69.2-37.6% in this case) is therefore large and needs to be taken into account in risk assessment.

Pollution characteristics and affecting factors of phthalate esters in agricultural soils in mainland China.

Phthalate esters (PAEs), the most commonly produced and used plasticizers, are widely used in plastic products and agroecosystems, posing risks to agricultural products and human health. However, current research on PAE pollution characteristics in agricultural soils in China is not comprehensive; affecting factors and relationships with microplastics and plasticizer organophosphate esters have not been sufficiently considered. In this study, farmland soil samples were collected with field questionnaires on a national scale across mainland China. The results showed that the detection rate of PAEs was 100% and the Σ16PAEs concentrations were 23.5 - 903 µg/kg. The level of PAEs was highest in the greenhouse, and significantly higher than that in mulched farmland (p < 0.05). The PAE concentration in northwestern China was the lowest among different physical geographic zones. PAEs in farmlands posed a low cancer risk to Chinese people. PAE pollution in farmlands was significantly (p < 0.05) affected by agronomic measures (such as disposal method), environmental factors, and socioeconomic factors. Overall, PAEs were significantly and positively correlated (p < 0.05) with organophosphate esters but not with microplastics. This study aims to provide scientific data for relevant prevention and control policies, as well as actionable recommendations for pollution reduction.

Impact of the simulated diagenesis on sorption of naphthalene and 1-naphthol by soil organic matter and its precursors.

Soil organic matter (SOM) in a peat soil, humic acid, and humin and their precursors (i.e., cellulose and lignin) were treated at high temperature (250 and 400 °C) with high pressure in a sealed platinum reaction kittle to simulate the influence of diagenesis on their composition and structure, and impact of the simulated diagenesis on sorption behaviors of hydrophobic organic compounds (HOCs) (i.e., naphthalene and 1-naphthol) by these samples was investigated. High temperature and pressure treatment greatly influenced chemical composition and physical properties of the original samples and their sorption for both naphthalene and 1-naphthol. Sorption of naphthalene by all samples was jointly regulated by hydrophobic and π-π interactions with their alkyl and aromatic carbon moieties, which was derived from the positive correlation between total hydrophobic carbon content of all sorbents and their organic carbon content-normalized sorption coefficients (Koc) for this compound (p = 0.075). However, sorption of 1-naphthol by the tested sorbents was governed by hydrogen bonding with their O-containing polar functionalities, as derived from the positive correlation between Koc values of 1-Naph and their polarity index ((O+N)/C). Difference in sorption mechanisms of naphthalene and 1-naphthol by the original and treated samples noted the great influence of chemical composition of sorbates on their interaction and essential roles of specific interactions (e.g., hydrogen bonding) in sorption of polar compound (i.e., 1-naphthol) to these sorbents. Surface area (SA) and porosity data of sorbents obtained from N2 sorption-desorption isotherms at 77 K showed that new SA and pores were created during the diagenetic process of all original samples, which provided substantial sorption sites and thus enhanced sorption of naphthalene and 1-naphthol. Among all tested samples, physicochemical properties of cellulose were most strongly affected by the simulated diagenetic process, and impact of such a process on its sorption intensity for the tested compounds was the most significant. The characterization data of the treated sorbents showed that the high temperature and pressure treatment similarly simulated the naturally occurring diagenesis of SOMs and their precursors, which is a first attempt. These findings are valuable for better understanding of the sorption behaviors of HOCs to SOM and its precursors as affected by diagenesis, which in turn is critical for elucidating the transport and fate of HOCs in the environment.

Status, characteristics, and ecological risks of microplastics in farmland surface soils cultivated with different crops across mainland China.

Microplastics (MPs) in agricultural soils could affect the safety of food crops. However, most relevant studies have paid scant attention to the crop fields and focused more on MPs in farmlands with or without film mulching in different regions. To detect MPs, we investigated farmland soils with >30 typical crop species from 109 cities in 31 administrative districts across mainland China. The relative contributions of different MP sources in different farmlands were estimated in detail based on a questionnaire survey, and we also assessed the ecological risks of MPs. Our results indicated the order of MP abundances in farmlands with different crop types, namely fruit fields > vegetable fields > mixed crop fields > food crop fields > cash crop fields. For the detailed sub-types, the highest MP abundance was detected in grape fields, which was significantly higher than that in solanaceous & cucurbitaceous vegetable fields (ranked second, p < 0.05), whereas the MP abundance was lowest in cotton and maize fields. The total contributions of three potential sources, namely livestock and poultry manure, irrigation water, and atmospheric deposition to MPs, varied depending on the crop types in the farmlands. Owing to exposure to MPs, the potential ecological risks to agroecosystems across mainland China were not negligible, particularly in fruit fields. The results of the current study could provide basic data and background information for future ecotoxicological studies and relevant regulatory strategies.

Sorption of four hydrophobic organic compounds by three chemically distinct polymers: role of chemical and physical composition.

The sorption behavior of four hydrophobic organic contaminants (HOCs) (i.e., phenanthrene, naphthalene, lindane, and 1-naphthol) by three types of polymers namely polyethylene (PE), polystyrene (PS), and polyphenyleneoxide (PPO) was examined in this work. The organic carbon content-normalized sorption coefficients (K(oc)) of phenanthrene, lindane, and naphthalene by PEs of same composition but distinct physical makeup of domains increased with their crystallinity reduction (from 58.7 to 25.5%), suggesting that mobility and abundance of rubbery domains in polymers regulated HOC sorption. Cross-linking in styrene-divinylbenzene copolymer (PS2) created substantial surface area and porosity, thus, K(oc) values of phenanthrene, lindane, naphthalene, and 1-naphthol by PS2 were as high as 274.8, 212.3, 27.4, and 1.5 times of those by the linear polystyrene (PS1). The K(oc) values of lindane, naphthalene, and 1-naphthol by polar PPO were approximately 1-3 orders of magnitude higher than those by PS1, and PPO had comparable sorption for phenanthrene but higher sorption for naphthalene and 1-naphthol than PS2. This can be a result that a portion of O-containing moieties in PPO were masked in the interior part, while leaving the hydrophobic domains exposed outside, therefore demonstrating the great influence of the spatial arrangement of domains in polymers on HOC sorption.

Field-based measurements of major air pollutant emissions from typical porcelain kiln in China.

China has been famous for its porcelains for millennia, and the combustion processes of porcelain production emit substantial amounts of air pollutants, which have not been well understood. This study provided firsthand data of air pollutant emissions from biomass porcelain kilns. The emission factor of PM2.5 was 0.95 ± 1.23 g/kg during the entire combustion cycle, lower than that of biomass burning in residential stoves and coal burning in brick kilns, attributed to the removal effects of the long-distance transport in dragon kilns. The temporal trend of particle pollutants, including particulate matters (PMs) and particulate polycyclic aromatic hydrocarbons (PAHs) (low at ignition phase and high at the end) again indicated the removal effects of the special structure, while gaseous pollutants, such as gaseous PAHs, exhibited the opposite result. The GWC100 was estimated as 1.4 × 106 and 0.5 × 106 kg CO2e/yr for the scenarios in which 50% and 100% of the wood was renewable, respectively. The GWC100 of dragon kilns is nearly equal to that of 745 households using wood-fueled stoves. These results indicate the necessity of pollution controls for biomass porcelain kilns to estimate the emission inventory and climate change.

Release kinetics as a key linkage between the occurrence of flame retardants in microplastics and their risk to the environment and ecosystem: A critical review.

The widely occurring debris of plastic materials, particularly microplastics, can be an important source of flame retardants, which are one of the main groups of chemicals added in the production of plastics from polymers. This review provides an overview on the use of flame retardants in plastic manufacturing, the kinetics of their releases from microplastics, the factors affecting their releases, and the potential environmental and ecosystem risk of the released flame retardants. The releases of flame retardants from microplastics typically involve three major steps: internal diffusion, mass transfer across the plastic-medium boundary layer, and diffusion in the environmental medium, while the overall mass transfer rate is commonly controlled by diffusion within the plastic matrix. The overall release rates of additive flame retardants from microplastics, which are dependent on the particle's geometry, can often be described by the Fick's Law. The physicochemical properties of flame retardant and plastic matrix, and ambient temperature all affect the release rate, which can be predicted with empirical and semi-empirical models. Weathering of microplastics, which reduces their particle sizes and likely disrupts their polymeric structures, can greatly accelerate the releases of flame retardants. Flame retardants could also be released directly from the microplastics ingested by aquatic organisms and seabirds, with physical and chemical digestion in the bodies significantly enhancing their release rates. Limited by the extremely slow diffusion in plastic matrices, the fluxes of flame retardants released from microplastics are very low, and are unlikely to pose significant risk to the ecosystem in general. More research is needed to characterize the mechanical, chemical, and biological processes that degrade microplastics and accelerate the releases of flame retardants and to model their release kinetics from microplastics, while efforts should also be made to develop environmentally benign flame retardants to ultimately minimize their risk to the environment and ecosystem.

Occurrence and characteristics of microplastics in the Haihe River: An investigation of a seagoing river flowing through a megacity in northern China.

Freshwater systems serve as important sources and transportation routes for marine microplastic pollution, and inadequate attention has been paid to this situation. Data on microplastic pollution of typical seagoing rivers in northern China are lacking. In the current study, we investigated the distribution and characteristics of microplastics in the main stream of the Haihe River, which flows through a metropolis with a high population density and level of industrialization and then flows into the Bohai Sea. The microplastic samples were collected by manta trawls with pore sizes of 333 µm, and the microplastic concentrations ranged from 0.69 to 74.95 items/m3. Fibers dominated in the surface water of the Haihe River; their shapes that were categorized as fibers, film, foam, fragments, and spheres, and contributed 17.4-86.7% of the total microplastics studied. The size distribution of the microplastics was concentrated in a range of 100-1000 µm, with 54.7% of the total sizes corresponding to the 333-µm trawl. Micro-Fourier transform infrared (µ-FT-IR) spectra showed that the main components were polyethylene, poly(ethylene-propylene) copolymer, and polypropylene. Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) measurements revealed scratches, micropores, and cracks on the surfaces of the microplastics due to mechanical friction, chemical oxidation and degradation processes. The results of this study confirmed the high abundance and high diversity of microplastics in an urban river and indicated appreciable impacts from point-source inputs on the microplastic pollution, such as effluents from wastewater treatment plants (WWTPs).

Releases of brominated flame retardants (BFRs) from microplastics in aqueous medium: Kinetics and molecular-size dependence of diffusion.

Microplastics (<5 mm) are increasingly detected in aquatic environment, and the high levels of brominated flame retardants (BFRs) contained in them can potentially impact water quality. This study characterized the release kinetics of polybrominated diphenyl ethers (PBDEs) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) from millimeter-sized microplastic pellets in water at environmentally relevant temperatures. Leaching rates of BFRs from the microplastic pellets made of acrylonitrile butadiene styrene (ABS) were found to be controlled by their diffusion within the plastic matrix, and their diffusion coefficients (D) in the plastic matrices ranged from 10-28.30 to 10-20.84 m2 s-1. The apparent activation energies of the BFRs' diffusion coefficients were estimated to be in the range of 64.1-131.8 kJ mol-1 based on their temperature dependence and the Arrhenius equation. The diffusion coefficients of the BFRs decrease with their molecular diameters, while the activation energies for diffusion increase with the molecular diameters, which are indicative of significant steric hindrance for BFR diffusion within the plastic matrices. A semi-empirical linear relationship was observed between Log10D and the glass transition temperature (Tg) of plastics, which allows prediction of the diffusion coefficients of BFRs in other types of microplastics commonly found in marine environment. The half-lives of BFR leaching (i.e., 50% depletion) from the microplastic pellets would range from tens of thousands to hundreds of billions of years at ambient temperatures if their physical and chemical structures could remain intact. Although the release fluxes of BFRs from microplastics are extremely low under the model conditions, a range of physical and chemical processes in the natural environment and the digestive systems of organisms that ingested them could potentially accelerate their leaching by causing breakdown and swelling of the plastic matrices.

The contribution of the Beijing, Tianjin and Hebei region's iron and steel industry to local air pollution in winter.

The Beijing, Tianjin and Hebei region (BTH) in China is a highly populated area that has recently experienced frequent haze episodes in winter. With high production capacities, the iron and steel industry (ISI) has long been a key source of air pollutants in BTH and is thus considered responsible for the degradation of local air quality. Here, we conducted a cross-disciplinary research combining the Weather Research and Forecasting with Chemistry (WRF/Chem) model, the multiregional input-output model (MRIO) and the health assessment model to explore the impacts of the ISI on air pollution in the BTH region in January 2012. Our results show large increases in air pollution due to direct ISI emissions, with up to a 90 µg/m3 monthly average of fine particulate matter (PM2.5) and sulfur dioxide (SO2) in eastern Tangshan and western Handan. In addition to direct emissions, the ISI has induced large quantities of indirect emissions from upstream sectors (e.g., the electricity and transportation sectors), leading to PM2.5, SO2 and NOx increases of 2-10 µg/m3 in BTH. Considering the direct and indirect emissions, we estimated that 275 (233-313) PM2.5-related mortalities occurred in January, and approximately 42% of these premature deaths occurred in Tangshan. A high rate of premature deaths also occurred in urban Beijing due to its high population density. Revealing the great health burden caused by the ISI, our results underscore the necessity for the Chinese government to reduce air pollutant emissions from the ISI and its upstream industries in BTH.

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement.

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.

Sorption mechanisms of sulfamethazine to soil humin and its subfractions after sequential treatments.

Sorption mechanisms of an antibiotic sulfamethazine (SMT) to humin (HM) isolated from a peat soil and its subfractions after sequential treatments were examined. The treatments of HM included removal of ash, O-alkyl carbon, lipid, and lignin components. The HF/HCl de-ashing treatment removed a large amount of minerals (mainly silicates), releasing a fraction of hydrophobic carbon sorption domains that previously were blocked, increasing the sorption of SMT by 33.3%. The de-O-alkyl carbon treatment through acid hydrolysis greatly reduced polarity of HM samples, thus weakening the interaction between sorbents with water at the interfaces via H-bonding, leaving more effective sorption sites. Sorption of SMT via mechanisms such as van der Waals forces and π-π interactions was enhanced by factors of 2.04-2.50. After removing the lipid/lignin component with the improved Soxhlet extraction/acid hydrolysis, the organic carbon content-normalized sorption enhancement index Eoc was calculated. The results demonstrated that the Eoc-lipid for SMT (16.9%) was higher than Eoc-lignin (10.1%), implying that removal of unit organic carbon mass of lipid led to a higher increase in sorption strength than that of lignin. As each component was progressively removed from HM, the sorption strength and isotherm nonlinearity of the residual HM samples for SMT were gradually enhanced. The Koc values of SMT by HM samples were positively correlated with their aromatic carbon contents, implying that π-π electron donor-acceptor interactions between the benzene ring of sorbate and the aromatic domains in HM played a significant role in their interactions.

Numerical simulation of PAHs sorption/desorption on soil with the influence of Tween80.

In this paper, the influences of inionic surfactant Tween80 on polycyclic aromatic hydrocarbons (PAHs) sorption/desorption on artificially contaminated soil were studied, and gamma model was applied to simulate the influences. Results showed that, with the use of Tween 80, the sorption behaviors of PAHs on soil altered significantly. Adsorbed Tween 80 increased the sorption amount of PAHs while the dissolved Tween80 increased the apparent solubility of PAHs. These two processes exert influences on the sorption coefficient of PAHs in soil-water system, which can be depicted by apparent sorption coefficient. The partition coefficients (the soil/water partition coefficient of PAHs and surfactants obtained from sorption experiments) and statistical parameters used in the amended gamma model were obtained in independent experiments. With these parameters, the gamma model could provide a satisfactory independent prediction of PAHs release from soil to aqueous phase at two surfactant concentrations.