Kai Liu

Status, Influences and Risk Assessment of Hexachlorocyclohexanes in Agricultural Soils Across China

Large amounts of hexaclorocyclohexanes (HCHs) were historically applied to Chinese soils. However, there has been limited information on the residue patterns of HCHs in soils at a national scale in China. In this study, surface soil samples were collected from agricultural fields across China, and the concentrations of HCHs and enantiomeric fractions (EFs) of α-HCH were measured. The results showed that the average concentrations of α-HCH, β-HCH, γ-HCH, and total HCHs in Chinese agricultural soils were 0.190, 1.31, 0.236, and 1.74 ng g(-1), respectively. Residues of HCHs likely originated from past usage of technical HCHs. The isomers of α-HCH and γ-HCH tended to accumulate in the sites with lower total HCH concentrations, lower temperature, higher elevation, and less wet precipitation when compared to β-HCH. Enantiomeric analysis showed a preferential degradation of (-)-α-HCH. Human health risks via various exposure routes to HCHs in soils were further estimated. Overall, the mean hazard index (HI) linked to noncarcinogenic risks was below 1, suggesting an absence of noncarcinogenic risks of HCHs in Chinese soils. In addition, the cancer risk values were all below 10(-4), which indicates low or very low risks.

Arsenic in agricultural soils across China: Distribution pattern, accumulation trend, influencing factors, and risk assessment

Arsenic (As) in the environment is of concern due to its strong toxicity and high risks to the ecosystems and humans. In this study, soil samples across China collected in 2011 and 2016 were used to determine the concentrations of arsenic in arable soils. The median concentration of arsenic in surface soils was 9.7mg/kg. The inventory of arsenic in the Chinese agricultural surface soils was estimated to be 3.7×106tons. In general, arsenic contamination was found higher in South and Northeast China than in other regions, with means of 18.7 and 15.8mg/kg, respectively. Vertically, arsenic concentrations were higher in top layer (0-15cm) soils (median of 9.8mg/kg) and decreased with soil depth (medians of 8.9mg/kg at 15-30cm and 8.0mg/kg at 30-45cm). By comparing with published data, an increasing accumulation trend over the past decades was found and this enhancement was positively related with the long-term application of fertilizers in agricultural practice, especially phosphate fertilizers. Soil pH was found to affect the movement of arsenic in soil, and high-pH conditions enhanced the pool of arsenic. The ecological risk assessment revealed that arsenic in Chinese agricultural soil posed a low risk to the ecosystem. Regarding human health, the mean hazard indices (HIs) of arsenic were below 1, suggesting an absence of non-carcinogenic risks. In addition, the cancer risks of arsenic in all soil samples were within the acceptable range (below 1×10-4), indicating low to very low risks to the exposed population. Findings from this study are valuable to provide effective management options for risk avoidance and to control the persistent accumulation of arsenic in the agriculture sector across the world.

Enantioseparation of four amide herbicide stereoisomers using high-performance liquid chromatography

The chirality of herbicides has been the focus of research. However, there is little information on the enantioseparation of amide herbicides with different chiral elements. In this study, the need for different chiral stationary phases (CSPs), mobile phases, temperatures and flow rates for the separation of napropamide, acetochlor and propisochlor was discussed in detail and compared to metolachlor. Resolution of C-chiral enantiomers was easier than that of axial-chiral enantiomers. Metolachlor and acetochlor could achieve baseline separation only on AY-H and AS-H columns, respectively. Propisochlor had satisfactory separations on OD-H and AS-H columns. Napropamide was separated on OJ-H, AY-H and AS-H columns. Both the structures of the compounds and CSPs and the interactions between them played significant roles in the enantioseparations. Molecule dockings were also used to elucidate the separation mechanisms. C-chiral enantiomers had perfect symmetry in their optical properties, whereas the axial-chiral enantiomers did not. The elution order for napropamide, acetochlor and propisochlor, with a single chiral location, was R- prior to S-. These results were the first that compare the enantioseparations of four amide herbicides with different chirality, and they provided the absolute configurations for the herbicides. The paper also illustrated certain mechanisms for enantioseparations.

Enantioseparation of napropamide by supercritical fluid chromatography: Effects of the chromatographic conditions and separation mechanism

Supercritical fluid chromatography (SFC) is already used for enantioseparation in the pharmaceutical industry, but it is rarely used for the separation of chiral pesticides. Comparing with high performence liquid chromatography, SFC uses much more environmnetal friendly and economic mobile phase, supercritical CO2 . In our work, the enantioseparation of an amide herbicide, napropamide, using three different polysaccharide-type chiral stationary phases (CSPs) in SFC was investigated. By studying the effect of different CSPs, organic modifiers, temperature, back-pressure regulator pressures, and flow rates for the enantioseparation of napropamide, we established a rapid and green method for enantioseparation that takes less than 2xa0minutes: The column was CEL2, the mobile phase was CO2 with 20% 2-propanol, and the flow rate was 2.0xa0mL/min. We found that CEL2 demonstrated the strongest resolution capability. Acetonitrile was favored over alcoholic solvents when the CSP was amylose and 2-propanol was the best choice when using cellulose. When the concentration of the modifiers or the flow rate was decreased, resolutions and analysis times increased concurrently. The temperature and back-pressure regulator pressure exhibited only minor influences on the resolution and analysis time of the napropamide enantioseparations with these chiral columns. The molecular docking analysis provided a deeper insight into the interactions between the enantiomers and the CSPs at the atomic level and partly explained the reason for the different elution orders using the different chiral columns.

Enantioselective effects of chiral amide herbicides napropamide, acetochlor and propisochlor: The more efficient R-enantiomer and its environmental friendly

Amide herbicides, which are used extensively worldwide, are often chiral. Enantiomeric selectivity comes from the different effects of the enantiomers on target and non-target organisms. In this study, the enantiomers of three amide herbicides were purified by the semi-preparative column and were used to investigate the enantioselective effects on target Echinochloa crusgalli (lowland rice weeds), and non-target Microcystis aeruginosa, and the yeast transformed with the human TRβ plasmid organisms. The results showed that (i) the R-enantiomers of the three amide herbicides exhibited the strongest activity toward weed inhibition and the lowest toxicity toward non-target organisms; (ii) napropamide was better suited for controlling root growth, while acetochlor and propisochlor were better for leaves control; (iii) herbicides at certain low concentrations (0.01u202fmgu202fL-1 for acetochlor and propisochlor) could be utilized to promote plant growth. These findings encourage the use of R-amide herbicides instead of their racemates to increase the efficiency of weed control and reduce the risk to non-target organisms. On the other hand, the adverse effects are caused mostly by S-enantiomer, using R-enantiomer-enriched products may offer great environmental/ecological benefits.

Activity, toxicity, molecular docking, and environmental effects of three imidazolinone herbicides enantiomers

All imidazolinone (IMI) herbicides are chiral consisting of two enantiomers; however, studies on the enantioselectivities of their interactions are limited. This study is a systematic assessment of the enantiomers and racemates of IMI herbicides, including semi-preparation and determination of absolute configurations, stereoselective bioactivity toward target organisms (Echinochloa crus-galli and Microcystis aeruginosa), and toxicity toward Michigan Cancer Foundation-7 (MCF-7) cells. R-imidazolinones were found to be more active than S-IMIs in the inhibition of target organisms, and neither enantiomer had estrogenic activity. Moreover, the relationship between the molecular structures and the efficiency of target growth inhibition by the IMI herbicides was investigated. Molecular modeling provided the rational structural basis for the enantioselectivity of the acetohydroxyacid synthase (AHAS) activity of the IMIs. These findings encourage the application of enantiopure R-IMI herbicides to capitalize on their advantages over the racemates.

Enantiomeric characterization of herbicide lactofen: Enantioseparation, absolute configuration assignment and enantioselective activity and toxicity

Chiral herbicides consist of two or more enantiomers, which usually differ in their biological properties and behave enantioselectively in biochemical process. Scant studies have been published in the past decades to characterize the enantiomers of herbicide lactofen. In this study, a laboratory method was developed to prepare the lactofen enantiomers using normal phase high performance liquid chromatography with an AD-H column, and μg level production yield was achieved in a single run. The two separated enantiomers had purity of ≫99%, with their absolute configurations assigned by experimental and calculated electronic and vibrational circular dichroism. Spectral analyses including semi-empirical rules as well as comparisons with the results of quantum chemical calculations confirmed the molecular configurations of R-lactofen and S-lactofen, in this elution order. The enantioselective bioactivity toward weed (Echinochloa crusgalli) and toxicity toward aquatic algae (Microcystis aeruginosa) was assessed by measuring their growth rates after the treatments with lactofen enantiomers and racemate. The results showed that R-lactofen affected E.xa0crusgalli more severely, while S-lactofen was more toxic to algae. Using active enantiomer instead of racemate may be more efficient and safe. Therefore, a more comprehensive understanding of the behaviors of chiral enantiomers is a need to improve activity and risk assessment and regulations of chiral compounds. Our work will be helpful to easily prepare single enantiomers from racemic mixtures and to establish effective absolute configurations of the enantiomers.

Environmental exposure to DDT and its metabolites in cord serum: Distribution, enantiomeric patterns, and effects on infant birth outcomes

Previous in vivo studies have suggested that prenatal exposure to dichlorodiphenyltrichloroethane (DDT) is endocrine disrupting, and may cause adverse health risks to newborns. In this cross-sectional study, non-invasive cord serum samples were collected from maternal-neonate pairs of an island population. Concentrations of DDT and its metabolites were analyzed to provide insights into the environmental exposure patterns and to elucidate their effects on birth outcomes. The average concentrations of p,p-DDE, o,p-DDD, p,p-DDD, o,p-DDT, p,p-DDT and total DDTs were 0.463, 0.293, 0.089, 0.098, 0.441 and 1.384μgg-1 lipid weight, respectively. Several maternal characteristics were identified as influencing factors on the environmental exposure distribution. The isomer ratios of individual components and the enantiomeric patterns of o,p-DDD and o,p-DDT indicated that historical technical DDT remains the predominant exposure source, though new sources of dicofol-type of DDT pollution must not be ignored. Using multivariable linear regression, increasing p,p-DDD and p,p-DDT levels were found to be significantly associated with an increase in neonatal birth weight, which deserves additional attention to obesity risks. No other birth outcome was found to be significant regarding DDT exposure. These findings raise the awareness of the prenatal risk of DDT and its metabolites among infants in contaminated areas.

Status of mercury accumulation in agricultural soil across China: Spatial distribution, temporal trend, influencing factor and risk assessment

Given its wide distribution in the natural environment and global transport potential, mercury (Hg) is regarded as a ubiquitous pollutant. In this study, we carried out nation-wide sampling campaigns across China to investigate the distribution of Hg in agricultural soils. Concentrations of Hg in the soils collected in 2011 and 2016 ranged from 0.04 to 0.69 and 0.06-0.78u202fmgu202fkg-1, respectively. Based on the data from 2016, the reserve of Hg in the surface arable soils (0-20u202fcm) in China was 4.1u202f×u202f104 metric tons and Chinese cultivated soils accounted for 63.4-364 metric tons of Hg released to the global atmosphere. The soil Hg concentrations were significantly higher than the reference background level, highlighting the impacts of anthropogenic activities. The vertical distribution pattern showed a clear enrichment at the surface and a decrease with depth of the soils. Comparison of calculated geo-accumulation indexes among individual provinces showed that Northwest China had higher levels of Hg contamination than other regions of China, likely due to long-term energy related combustions in the area. Soil Hg level showed strong positive correlations with organic matter contents of soil, as well as the mean annual precipitation and temperature of the sampling locations. The non-carcinogenic human health risks of soil Hg were below the threshold level, but the general risk to the ecosystem was considerable. The increases in Hg accumulation from 2011 to 2016u202fat provincial level were found to relate to coal combustion, power generation and per capita GDP. This examination of energy consumption and socioeconomic drivers for Chinas soil Hg reserve increase is critical for direct Hg control by guiding policy-making and targets of technology development in era of rapid economic growth.

Enantioselectivity in biotransformation and bioaccumulation processes of typical chiral contaminants

Chirality is a critical topic in the medicinal and agrochemical fields. One quarter of all agrochemicals was chiral in 1996, and this proportion has increased remarkably with the introduction of new compounds over time. Despite scientists have made great efforts to probe the enantiomeric selectivity of chiral chemicals in the environment since early 1990s, the different behaviours of individual enantiomers in biologically mediated processes are still unclear. In the present review, we highlight state-of-the-knowledge on the stereoselective biotransformation and accumulation of chiral contaminants in organisms ranging from invertebrates to humans. Chiral insecticides, fungicides, and herbicides, polychlorinated biphenyls (PCBs), pharmaceuticals, flame retardants hexabromocyclododecane (HBCD), and perfluorooctane sulfonate (PFOS) are all included in the target compounds. Key findings included: a) Changes in the enantiomeric fractions inxa0vitro and inxa0vivo models revealed that enantioselectivity commonly occurs in biotransformation and bioaccumulation. b) Emerging contaminants have become more important in the field of enantioselectivity together with their metabolites in biological transformation process. c) Chiral signatures have also been regarded as powerful tools for tracking pollution sources when the contribution of precursor is unknown. Future studies are needed in order to understand not only preliminary enrichment results but also detailed molecular mechanisms in diverse models to comprehensively understand the behaviours of chiral compounds.