Insight study of rare earth elements in PM2.5 during five years in a Chinese inland city: Composition

The booming development of rare earth industry and the extensive utilization of its products accompanied by urban development have led to the accelerated accumulation of rare earth elements (REEs) as emerging pollutants in atmospheric environment.In this study,the variation of REEs in PM_2.5with urban (a non-mining city) transformation was investigated through five consecutive years of sample collection.The compositional variability and provenance contribution of REEs in PM_2.5     

Does the long-term application of calcium superphosphate lead to an increase of the soil rare earth element contents?

In order to test whether the long-term application of calcium superphosphate leads to an increase of the soil rare earth element contents, superphosphate fertilized soils were sampled and compared with superphosphate-free soils. Spectrophlame inductively coupled argon plasma atomic emission spectrophotometer （ICP-AES） was applied to quantify the rare earth elements （REEs）. The total rare earth element contents in calcium superphosphate from Zhijin County, west part of Guizhou Province, China （produced by the sulphuric acid treatment of the apatites） are about 2.54 mg/g. Between 38 and 189 gREEs/hm^2 per year （available for plants, estimated by 2% citric acid） will be introduced into the soil solution when applying 320 kg superphosphate/hm^2 per year. The long-term application of the latter will increase the REE content by about 18% in the soil surface layer in these areas. A statistically significant increase of the content of the rare earths in some cultivated soils should not be neglected.     

Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.     

The effect of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ) and Pb(Ⅱ) adsorption

The effects of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ)and Pb(Ⅱ)adsorption were investigated.After combination with DBM,the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of kaolinite and goethite improved compared with the application of the minerals independently.The modeling results of potentiometric titration data proved that the site concentrations of kaolinite and goethite increased by 80%and 30%,respectively after combination with DBM.However,the involvement of functional groups in the DBM/mineral combinations resulted in lower concentrations of observed sites than the theoretical values and led to the enhancement of desorption rates by NH_4NO_3 and EDTA-Na_2.The DBM-mineral complexes might also help to prevent heavy metals from entering DBM cells to improve the survivability of DBM in heavy metal-contaminated environments.During the combination process,the extracellular proteins of DBM provided more binding sites for the minerals to absorb Cu(Ⅱ)and Pb(Ⅱ).In particular,an especially stable complexation site was formed between goethite and phosphodiester bonds from EPS to enhance the Pb(Ⅱ)adsorption capacity.So,we can conclude that the DBM–mineral complexes could improve the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of minerals and protect DBM in heavy metal-contaminated environments.     

Flocculating characteristic of activated sludge flocs: Interaction between Al3+ and extracellular polymeric substances

Aluminum flocculant can enhance the flocculating performance of activated sludge.However,the binding mechanism of aluminum ion(Al 3+) and extracellular polymeric substances(EPS) in activated sludge is unclear due to the complexity of EPS.In this work,threedimensional excitation emission matrix fluorescence spectroscopy(3DEEM),fluorescence quenching titration and Fourier transform infrared spectroscopy(FT-IR) were used to explore the binding behavior and mechanism between Al 3+ and EPS.The results showed that two fluorescence peaks of tyrosineand tryptophan-like substances were identified in the loosely bound-extracellular polymeric substances(LB-EPS),and three peaks of tyrosine-,tryptophanand humic-like substances were identified in the tightly boundextracellular polymeric substances(TB-EPS).It was found that these fluorescence peaks could be quenched with Al 3+ at the dosage of 3.0 mg/L,which demonstrated that strong interactions took place between the EPS and Al 3+.The conditional stability constants for Al 3+ and EPS were determined by the Stern-Volmer equation.As to the binding mechanism,the-OH,N-H,C=O,C-N groups and the sulfurand phosphorus-containing groups showed complexation action,although the groups in the LB-EPS and TB-EPS showed different behavior.The TB-EPS have stronger binding ability to Al 3+ than the LB-EPS,and TB-EPS play an important role in the interaction with Al 3+.     

Competitive and cooperative adsorption of arsenate and citrate on goethite

The fate of arsenic in natural environments is influenced by adsorption onto metal (hydr)oxides. The extent of arsenic adsorption is strongly a ected by coexisting dissolved natural organic acids. Recently, some studies reported that there existed competitive adsorption between arsenate and citrate on goethite. Humic acid is known to interact strongly with arsenate by forming complexes in aqueous solution, hence it is necessary to undertake a comprehensive study of the adsorption of arsenate/citrate onto goethite in the presence of one another. The results showed that at the arsenate concentrations used in this study (0.006–0.27 mmol/L), citrate decreased arsenate adsorption at acidic pH but no e ect was observed at alkaline pH. In comparison, citrate adsorption was inhibited at acidic pH, but enhanced at alkaline pH by arsenate. This was probably due to the formation of complex between arsenate and citrate like the case of arsenate with humic acid. These results implied that the mechanism of the adsorption of arsenate and citrate onto goethite in the presence of one another involved not only competition for binding sites, but the cooperation between the two species at the watergoethite interface as well.     

Relating Cd2 + binding by humic acids to molecular weight: A modeling and spectroscopic study

Molecular weight(Mw) is a fundamental property of humic acids(HAs), which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid(HA) extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna(NICA-Donnan) models combined with fluorescence excitation-emission matrix(EEM) quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd~(2+) to Mw fractions of HA followed the order UF1( 5 kDa) UF2(5–10 kDa) UF4( 30 kDa) UF3(10–30 kDa). Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd~(2+) among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd~(2+) to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.     

Toxicological effects involved in risk assessment of rare earth lanthanum on roots of Vicia faba L. seedlings

Combined chemical analyses and biological measurements were utilized to investigate potential toxicological effects and possible mechanisms involved in risk assessment of rare earth elements (REEs) on Vicia faba L. seedlings, which were hydroponically cultivated and exposed to various concentrations of lanthanum (La) for 15 days. The results showed that La contents in both the solution and roots increased with the increase of extraneous La, contributing to hormetic dose responses of superoxide dismutase (SOD), catalase (CAT), guaiacol peroxidase (GPX), ascorbate peroxidase (APX) and endoprotease (EP) isozymes activities, and HSP 70 production enhanced at low doses but suppressed at higher doses of La. These physiological responses constituted antioxidant and detoxification systems against La-induced oxidative stress. The elevated La levels also contributed to oxidatively modified proteins, which were most responsible for subsequent cell death and growth retardation of the roots. By combination of hormetic and traditional threshold dose levels, the threshold dose range was deduced to be 108-195 μg La/g dry weight in the roots, corresponding to 0.90-3.12 mg/L of soluble La in the culture solution. It suggests that persistent applications of REEs may lead to potential ecological risk in the environment.     

Formation process and mechanism of humic acid-kaolin complex determined by carbamazepine sorption experiments and various characterization methods

To explore the formation process and mechanism of organic matter and organic-mineral complex under humification and mineralization conditions, a series of samples including humic acid, kaolin, and humic acid-kaolin complex were prepared using a subcritical water treatment method(SWT) under specific temperature, pressure and reaction time conditions. HA was used as a surrogate for natural organic matter because it has a similar abundant pore structure,variety of carbon types, and chemical components. These samples were used in carbamazepine(CBZ) sorption experiments and characterized by a variety of techniques. The polymerization of humic acid under the conditions of increased temperature and pressure resulted in an increase in specific surface area and molecular quantity. In addition, the degree of aromaticity rose from59.52% to 70.90%. These changes were consistent with the transformation from ‘soft carbon' to‘hard carbon' that occurs in nature. The results of sorption experiments confirmed the interaction between humic acid and kaolin from the difference between the predicted and actual Qevalues. The conceptual model of humic acid-kaolin complex could be deduced and described as follows. Firstly, the aromatic components of humic acid preferentially combine with kaolin through the intercalation effect, which protects them from the treatment effects.Next, the free carboxyl groups and small aliphatic components of humic acid interact on the surface of kaolin, and these soft species transform into dense carbon through cyclization and polymerization. As a result, humic acid-kaolin complex with a mineral core and dense outer carbonaceous patches were formed.     

Adsorption of chloroacetanilide herbicides on soil (I). Structural influence of chloroacetanilide herbicide for their adsorption on soils and its components

Adsorption of chloroacetanilide herbicide acetochlor,alachlor, metolachlor and propachlor on soils and soil components was determined, and the structural differences of these herbicides were used to explain the order of sorptivity. Adsorption isotherms for all herbicide-soil combinations conformed to the Freundlich equation, and Kf increased with increasing soil organic carbon content. Kd on soil humic acid was greater than that on clay, but association of humic acid with clay reduced the overall adsorption. On all soils and soil humic acids, herbicide adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca²⁺-montmorrilonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR spectra of herbicide-clay or herbicide-humic acid-clay mixtures showed that H-bonding and charge transfer were the primary interaction pathways between these compounds and the surface of clay or humic acids. The different moieties attached to 2-chloro-acetanilide and their unique arrangement may have influenced the binding mechanisms and thus the sorptivity of these herbicides. This study indicates that the structural difference of pesticides in the same classes may be used as a molecular probe to obtain a better understanding of sorption mechanisms of pesticides on soil.     

Effect of environmental factors on the complexation of iron and humic acid

A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron (Fe) and humic acid (HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, pH, temperature and UV radiation, were investigated. The Fe-HA complex residence time was also studied. Experimental results showed that pH could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of NaCl. Temperature had some influence on the complexation. The yield of Fe-HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe-HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe-HA complex residence time was about 20 hr. Complexation of Fe and HA reached a maximum level under the conditions of pH 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe-HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher pH and ionic strength in an estuary, the concentration of the Fe-HA complex would decrease.     

Characteristics of isothermal adsorption and desorption of aluminum ion to/from humic acids

The adsorption and desorption characteristics of Al3+ to/from humic acids at di erent pH, ionic strength, and temperature were studied by the C-25 glucosan-gel chromatography method. The results showed that the maximum adsorption amount (Qmax) and adsorption constant (k) increased, whereas, the absolute value of standard thermodynamic molar free energy change ( G0 m) decreased with the increase of pH at constant ionic strength and temperature. With ionic strength increasing from 0 to 0.15 mol/L, Qmax and k increased and the absolute value of G0 m decreased at constant pH and temperature. High temperature was unfavorable for the adsorption reaction, as indicated by the dramatic decrease of Qmax and the absolute value of G0 m with an increase in temperature. The standard thermodynamic molar free energy change ( G0 m) and the standard thermodynamic enthalpy change ( H0m ) of the adsorption reaction were both negative, suggesting that adsorption reaction was spontaneous and exothermic. The desorption rate of HA-Al3+ complex accelerated with the decrease of pH, and a significant linear relationship could be obtained between pH and the desorption rates of Al3+ from humic acids. These results demonstrated that the Al3+ adsorption reaction was a “biphase” reaction, and adsorption occurred at both the interior and exterior adsorption sites of humic acids.     

Effect of environmental factors on the complexation of iron and humic acid

A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron(Fe) and humic acid(HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, p H, temperature and UV radiation, were investigated. The Fe–HA complex residence time was also studied. Experimental results showed that p H could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of Na Cl. Temperature had some influence on the complexation. The yield of Fe–HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe–HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe–HA complex residence time was about 20 hr.Complexation of Fe and HA reached a maximum level under the conditions of p H 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe–HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher p H and ionic strength in an estuary, the concentration of the Fe–HA complex would decrease.     

Modeling of acute cadmium toxicity in solution to barley root elongation using biotic ligand model theory

Protons（H⁺）as well as different major and trace elements may inhibit cadmium（Cd）uptake in aquatic organisms and thus alleviate Cd toxicity.However,little is known about such interactions in soil organisms.In this study,the independent effects of the cations calcium(Ca²⁺),magnesium(Mg²⁺),potassium（K⁺）,H+and zinc(Zn²⁺)on Cd toxicity were investigated with 5-day long barley root elongation tests in nutrient solutions.The tested concentrations of selected cations and trace metal ions were based on the ranges that occur naturally in soil pore water.The toxicity of Cd decreased with increasing activity of Ca²⁺,Mg²⁺,H⁺and Zn²⁺,but not K⁺.Accordingly,conditional binding constants were obtained for the binding of Cd²⁺,Ca²⁺,Mg²⁺,H⁺,and Zn²⁺ with the binding ligand:log K_CdBL5.19,logK_CaBL2.87,logK_MgBL2.98,logK_HBL5.13 and logK_ZnBL5.42,respectively.Furthermore,it was calculated that on average 29% of the biotic ligand sites needed to be occupied by Cd to induce a 50% decrease in root elongation.Using the estimated constants,a biotic ligand model was successfully developed to predict the Cd toxicity to barley root elongation as a function of solution characteristics.The feasibility and accuracy of its application for predicting Cd toxicity in soils were discussed.     

Removal of arsenate with hydrous ferric oxide coprecipitation：Effect of humic acid

Insights from the adverse effect of humic acid(HA) on arsenate removal with hydrous ferric oxide(HFO) coprecipitation can further our understanding of the fate of As(V) in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As(V) on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering(SERS), extended X-ray absorption fine structure(EXAFS) spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared(ATR-FTIR) measurement, and charge distribution multisite complexation(CDMUSIC) modeling. The As(V) removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As(V) mass concentration. The SERS analysis excluded the HA-As(V) complex formation. The EXAFS results indicate that As(V) formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26–3.31 ?. The in situ ATR-FTIR measurements show that As(V) replaces surface hydroxyl groups and forms innersphere complex. High concentrations of HA may physically block the surface sites and inhibit the As(V) access. The adsorption of As(V) and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As(V) and HA reasonably well.     

Trace elements and stable sulfur isotopes in plants of acid mine drainage area: Implications for revegetation of degraded land

The abundances of trace elements, a low pH of water and soil in areas impacted by the acid mine drainage (AMD) may cause an excessive uptake of potentially toxic elements and nutritional imbalances in plants. Metal-tolerant, native plants are used for revegetation of degraded mining areas. We established levels of selected trace elements and stable sulfur isotopes in the above-ground plant biomass collected in a mining area in south-central Poland. In 2016, 20 samples of the most common species were collected from sites with a different influence of acid mine drainage and analyzed for trace elements by the inductively coupled plasma mass spectrometry technique. On the basis of the results obtained in 2016, the most contaminated site was selected for a more detailed study, in which sulfur contents and stable sulfur isotope ratios were determined together with trace elements in 17 samples. The results confirmed that the plants native to the AMD area efficiently accumulated trace elements, especially As and rare earth elements. Mosses showed the highest content of trace elements, but exhibited the lowest concentrations of sulfur accompanied by the highest δ³⁴S values. It has been shown for the first time that stable sulfur isotope composition of AMD plants in south-central Poland is significantly depleted in the ³⁴S isotope showing an average δ³⁴S value of –10.5‰ in comparison with positive δ³⁴S values in local vegetation growing outside the AMD area and in local precipitation.     

Simultaneous elution of polycyclic aromatic hydrocarbons and heavy metals from contaminated soil by two amino acids derived from β-cyclodextrins

Two highly water-soluble amino acids, which derived from -CDs, i.e., glutamic acid- -cyclodextrin (GluCD) and ethylene-diamine- -cyclodextrin (EDCD), were synthesized and were examined for their e ect on solubilization of anthracene (ANT), complexation of cadmium (Cd2+), and elution removal of ANT and Cd2+ in soil. The results showed that GluCD and EDCD were powerful complexant for ANT and Cd2+. In the presence of 10 g/L GluCD and EDCD, the solubilization of ANT increased by 47.04 and 23.85 times compared to the control, respectively. GluCD resulted in approximately 90% complexation of Cd2+ while 70% complexation was observed for EDCD. Simultaneously, GluCD and EDCD could greatly enhance the elution removal of ANT and Cd2+ from soil. GluCD resulted in the highest elution e ciency of ANT and Cd2+.With the addition of 10 g/L GluCD, 53.5% of ANT and 85.6% of Cd2+ were eluted, respectively. The ANT had a negligible e ect on the Cd2+ removal due to di erent complexing sites of ANT and Cd2+, while Cd2+ enhanced the ANT removal under the addition of GluCD because Cd2+ neutralized the –COOH group of GluCD. Adversely, the removal of ANT was decreased with Cd2+ under the addition of EDCD, this was due to the fact that Cd2+ enhanced the polarity of EDCD molecule and inhibited the complexation between ANT and EDCD. The study suggested that GluCD could be preferred and be successfully applied to remediation of heavy metals or organic compounds in contaminated soil.     

Simultaneous elution of polycyclic aromatic hydrocarbons and heavy metals from contaminated soil by two amino acids derived from β-cyclodextrins

Two highly water-soluble amino acids,which derived from β-CDs,i.e.,glutamic acid-β-cyclodextrin (GluCD) and ethylene-diamineβ-cyclodextrin (EDCD),were synthesized and were examined for their effect on solubilization of anthracene (ANT),complexation of cadmium (Cd2+),and elution removal of ANT and Cd2+ in soil.The results showed that GluCD and EDCD were powerful complexant for ANT and Cd2+.In the presence of 10 g/L GluCD and EDCD,the solubilization of ANT increased by 47.04 and 23.85 times compared to the control,respectively.GluCD resulted in approximately 90% complexation of Cd2+ while 70% complexation was observed for EDCD.Simultaneously,GluCD and EDCD could greatly enhance the elution removal of ANT and Cd 2+ from soil.GluCD resulted in the highest elution efficiency of ANT and Cd2+.With the addition of 10 g/L GluCD,53.5% of ANT and 85.6% of Cd2+ were eluted,respectively.The ANT had a negligible effect on the Cd2+ removal due to different complexing sites of ANT and Cd2+,while Cd2+ enhanced the ANT removal under the addition of GluCD because Cd2+ neutralized the-COOH group of GluCD.Adversely,the removal of ANT was decreased with Cd2+ under the addition of EDCD,this was due to the fact that Cd2+ enhanced the polarity of EDCD molecule and inhibited the complexation between ANT and EDCD.The study suggested that GluCD could be preferred and be successfully applied to remediation of heavy metals or organic compounds in contaminated soil.     

A simulation study of mercury release fluxes from soils in wet-dry rotation environment

A simulative mesocosm study was conducted to evaluate the influence of wet-dry rotation on mercury（Hg） flux from soil/water to air and the distribution of Hg species in water as well as Hg chemical fractions in soil. Three types of soil were employed including two kinds of paddy soil, Typic Purpli-Udic Cambosols（TPUC） and Xanthi-Udic Ferralosols（XUF）, as well as the Alluvial Soil（AS） from Three Gorge reservoir area in Chongqing, China. The results showed that Hg fluxes in wetting periods were significantly higher than that in drying periods. It might be due to the formation of a layer of stable air over the water surface in which some redox reactions promote evasion processes over the water surface. This result indicated that more Hg would be evaporated from the Three Gorge reservoir and paddy soil field during the flooding season. Hg fluxes were positively correlated with air temperature and solar irradiation, while negatively correlated with air humidity and the electronic conductivity of water. Hg fluxes from AS and TPUC were significantly higher than that from XUF, which might be due to the higher organic matter（OM） contents in XUF than TPUC and AS. The reduction processes of oxidized Hg were restrained due to the strong binding of Hg to OM, resulting in the decrease in Hg flux from the soil.     

Oxidative capacities of size-segregated haze particles in a residential area of Beijing

The frequent haze days around the Chinese capital of Beijing in recent years have aroused great attention owing to the detrimental efects on visibility and public health. To discover the potential health efects of the haze, oxidative capacities of airborne particles collected in Beijing during haze and clear days were comparably assessed by a plasmid scission assay. Eleven water-soluble trace elements(As, Cd, Cr, Cu, Mn, Ni, Pb, V, Se, Tl, and Zn) in the size-segregated airborne particles were quantitatively analyzed by inductively coupled plasma mass spectrometry, and most of the watersoluble trace elements were found to mainly concentrate in the fine particle size of 0.56–1.0 μm. In comparison with clear days, the mass concentrations of 11 analyzed water-soluble trace elements remarkably increased during haze days, and the oxidative capacities determined by the plasmid scission assay were markedly elevated accordingly during the haze days under the same dosage of particles as for those during clear days. Water-soluble trace elements in airborne particles, such as Cu, V, and particularly Zn, were found to have significantly positive correlations with the plasmid DNA damage rates. Because Cu, V, and Zn have been considered as bioavailable elements, the evident increase of these elements during haze days may be greatly harmful to human health.