Yandi Hu

Health risk assessment of personal inhalation exposure to volatile organic compounds in Tianjin, China

Volatile Organic Compounds (VOCs) exposure can induce a range of adverse human health effects. To date, however, personal VOCs exposure and residential indoor and outdoor VOCs levels have not been well characterized in the mainland of China, less is known about health risk of personal exposure to VOCs. In this study, personal exposures for 12 participants as well as residential indoor/outdoor, workplace and in vehicle VOCs concentrations were measured simultaneously in Tianjin, China. All VOCs samples were collected using passive samplers for 5 days and were analyzed using Thermal Desorption GC-MS method. U.S. Environmental Protect Agencys Inhalation Unit Risks were used to calculate the inhalation cancer health risk. To assess uncertainty of health risk estimate, Monte Carlo simulation and sensitivity analysis were implemented. Personal exposures were greater than residential indoor exposures as expected with the exception of carbon tetrachloride. Exposure assessment showed modeled and measured concentrations are statistically linearly correlated for all VOCs (P<0.01) except chloroform, confirming that estimated personal exposure using time-weighted model can provide reasonable estimate of personal inhalation exposure to VOCs. Indoor smoking and recent renovation were identified as two major factors influencing personal exposure based on the time-activity pattern and factor analysis. According to the cancer risk analysis of personal exposure, benzene, chloroform, carbon tetrachloride and 1,3-butadiene had median upper-bound lifetime cancer risks that exceeded the U.S. EPA benchmark of 1 per one million, and benzene presented the highest median risks at about 22 per one million population. The median cumulative cancer risk of personal exposure to 5 VOCs was approximately 44 per million, followed by indoor exposure (37 per million) and in vehicle exposure (36 per million). Sensitivity analysis suggested that improving the accuracy of exposure measurement in further research would advance the health risk assessment.

Characterization of PM10 fraction of road dust for polycyclic aromatic hydrocarbons (PAHs) from Anshan, China

Nineteen road dust samples were collected during 2005 in different parts of the urban area of Anshan, Liaoning Province, China, and 11 polycyclic aromatic hydrocarbons (PAHs) species were quantitatively analyzed using GC-MS. The results indicated that the total average concentration of PAHs over the investigated sites ranged from 48.73 to 638.26 microg/g, with a mean value of 144.25 microg/g, higher than the concentrations measured in previous studies. PAHs concentrations were higher with high molecular weight homologues (4-6 rings PAHs), accounting for 83.24-96.98%, showing combustion of petroleum fuels was a potential source. Organic carbon in road dust was considered one of the important factors that influenced the concentrations of PAHs in this study, and it was found that concentrations of total PAHs were correlated with those of organic carbon in road dust. The results of diagnostic ratios analysis showed traffic emission (gasoline or diesel) was one of the most important sources of road dust PAHs. Principal component analysis (PCA) indicated that the major sources of road dust PAHs might be emission from traffic, steel industry, cooking and coal combustion.

Biotite―Brine Interactions under Acidic Hydrothermal Conditions: Fibrous Illite, Goethite, and Kaolinite Formation and Biotite Surface Cracking

To ensure safe and efficient geologic CO(2) sequestration (GCS), it is crucial to have a better understanding of CO(2)-brine-rock interactions under GCS conditions. In this work, using biotite (K(Mg,Fe)(3)AlSi(3)O(10)(OH,F)(2)) as a model clay mineral, brine-biotite interactions were studied under conditions relevant to GCS sites (95 °C, 102 atm CO(2), and 1 M NaCl solution). After reaction for 3-17 h, fast growth of fibrous illite on flat basal planes of biotite was observed. After 22-70 h reaction, the biotite basal surface cracked, resulting in illite detaching from the surface. Later on (96-120 h), the cracked surface layer was released into solution, thus the inner layer was exposed as a renewed flat basal surface. The cracking and detachment of the biotite surface layer increased the surface area in contact with solution and accelerated biotite dissolution. On biotite edge surfaces, Al-substituted goethite and kaolinite precipitated. In control experiments with water under the same temperature and pressure, neither macroscopic fibrous illite nor cracks were observed. This work provides unique information on biotite-brine interaction under acidic hydrothermal conditions.

Environmentally abundant anions influence the nucleation, growth, Ostwald ripening, and aggregation of hydrous Fe(III) oxides.

The simultaneous homogeneous and heterogeneous precipitation of hydrous Fe(III) oxides was investigated in the presence of environmentally ubiquitous anions (nitrate, chloride, and sulfate). Experiments were conducted with 10(-4) M Fe(III) at acidic pH (pH = 3.7 ± 0.2), which often occurs at acid mine drainage sites or geologic CO(2) storage aquifers near injection wells. Quartz was used as a model substrate for heterogeneous precipitation. Small angle X-ray scattering (SAXS) and grazing incidence SAXS (GISAXS), atomic force microscopy (AFM), and dynamic light scattering (DLS) measurements were conducted. In situ SAXS/GISAXS quantified the size, total particle volume, number, and surface area evolutions of the primary nanoparticles formed in the nitrate and chloride systems. In both systems, the heterogeneously precipitated particles were smaller than the homogeneously precipitated particles. Compared with chloride, the volume of heterogeneously precipitated hydrous Fe(III) oxides on the quartz surface was 10 times more in the nitrate system. After initial fast heterogeneous nucleation in both nitrate and chloride systems, nucleation, growth, and aggregation occurred in the nitrate system, whereas Ostwald ripening was the dominant heterogeneous precipitation process in the chloride system. In the sulfate system, fast growth of the heterogeneously precipitated particles and fast aggregation of the homogeneously precipitated particles led to the formation of particles larger than the detection limit of GISAXS/SAXS. Thus, the sizes of the particles precipitated on quartz surface and in solution were analyzed with AFM and DLS, respectively. This study provides unique qualitative and quantitative information about the location (on quartz surfaces vs in solutions), size, volume, and number evolutions of the newly formed hydrous iron oxide particles in the presence of quartz substrate and ubiquitous anions, which can help in understanding the fate and transport of pollutants in the environment.

Viability and Metal Reduction of Shewanella oneidensis MR-1 under CO2 Stress: Implications for Ecological Effects of CO2 Leakage from Geologic CO2 Sequestration

To study potential ecological impacts of CO(2) leakage to shallow groundwater and soil/sediments from geologic CO(2) sequestration (GCS) sites, this work investigated the viability and metal reduction of Shewanella oneidensis MR-1 under CO(2) stress. While MR-1 could grow under high-pressure nitrogen gas (500 psi), the mix of 1% CO(2) with N(2) at total pressures of 15 or 150 psi significantly suppressed the growth of MR-1, compared to the N(2) control. When CO(2) partial pressures were over 15 psi, the growth of MR-1 stopped. The reduced bacterial viability was consistent with the pH decrease and cellular membrane damage under high pressure CO(2). After exposure to 150 psi CO(2) for 5 h, no viable cells survived, the cellular contents were released, and microscopy images confirmed significant cell structure deformation. However, after a relatively short exposure (25 min) to 150 psi CO(2), MR-1 could fully recover their growth within 24 h after the stress was removed, and the reduction of MnO(2) by MR-1 was observed right after the stress was removed. Furthermore, MR-1 survived better if the cells were aggregated rather than suspended, or if pH buffering minerals, such as calcite, were present. To predict the cell viability under different CO(2) pressures and exposure times, a two-parameter mathematical model was developed.

Control of Heterogeneous Fe(III) (Hydr)oxide Nucleation and Growth by Interfacial Energies and Local Saturations

To predict the fate of aqueous pollutants, a better understanding of heterogeneous Fe(III) (hydr)oxide nucleation and growth on abundant mineral surfaces is needed. In this study, we measured in situ heterogeneous Fe(III) (hydr)oxide nucleation and growth on quartz, muscovite, and corundum (Al2O3) in 10(-4) M Fe(III) solution (in 10 mM NaNO3 at pH = 3.7 ± 0.2) using grazing incidence small-angle X-ray scattering (GISAXS). Interestingly, both the fastest heterogeneous nucleation and slowest growth occurred on corundum. To elucidate the mechanisms, zeta potential and water contact angle measurements were conducted. Electrostatic forces between the charged Fe(III) (hydr)oxide polymeric embryos and substrate surfaces-which affect local saturations near the substrate surfaces-controlled heterogeneous growth rates. Water contact angles (7.5° ± 0.7, 22.8° ± 1.7, and 44.8° ± 3.7 for quartz, muscovite, and corundum, respectively) indicate that corundum has the highest substrate-water interfacial energy. Furthermore, a comparison of structural mismatches between the substrates and precipitates indicates a lowest precipitate-substrate interfacial energy for corundum. The fastest nucleation on corundum suggests that interfacial energies in the solution-substrate-precipitate system controlled heterogeneous nucleation rates. The unique information provided here bolsters our understanding of nanoparticle-mineral surface interactions, mineral surface modification by iron oxide coating, and pollutant transport.

Fe(III) Hydroxide Nucleation and Growth on Quartz in the Presence of Cu(II), Pb(II), and Cr(III): Metal Hydrolysis and Adsorption

Fe(III) hydroxide nanoparticles are an essential carrier for aqueous heavy metals. Particularly, iron hydroxide precipitation on mineral surfaces can immobilize aqueous heavy metals. Here, we used grazing-incidence small-angle X-ray scattering (GISAXS) to quantify nucleation and growth of iron hydroxide on quartz in 0.1 mM Fe(NO3)3 solution in the presence of Na(+), Cu(2+), Pb(2+), or Cr(3+) at pH = 3.7 ± 0.1. In 30 min, the average radii of gyration (R(g)) of particles on quartz grew from around 2 to 6 nm in the presence of Na(+) and Cu(2+). Interestingly, the particle sizes remained 3.3 ± 0.3 nm in the presence of Pb(2+), and few particles formed in the presence of Cr(3+). Quartz crystal microbalance dissipation (QCM-D) measurements showed that only Cr(3+) adsorbed onto quartz, while Cu(2+) and Pb(2+) did not. Cr(3+) adsorption changed the surface charge of quartz from negative to positive, thus inhibiting the precipitation of positively charged iron hydroxide on quartz. Masses and compositions of the precipitates were also quantified. This study provided new insights on interactions among quartz, iron hydroxide, and metal ions. Such information is helpful not only for environmental remediation but also for the doping design of iron oxide catalysts.

Na+, Ca2+, and Mg2+ in Brines Affect Supercritical CO2–Brine–Biotite Interactions: Ion Exchange, Biotite Dissolution, and Illite Precipitation

For sustainable geologic CO(2) sequestration (GCS), a better understanding of the effects of brine cation compositions on mica dissolution, surface morphological change, and secondary mineral precipitation under saline hydrothermal conditions is needed. Batch dissolution experiments were conducted with biotite under conditions relevant to GCS sites (55-95 °C and 102 atm CO(2)). One molar NaCl, 0.4 M MgCl(2), or 0.4 M CaCl(2) solutions were used to mimic different brine compositions, and deionized water was used for comparison. Faster ion exchange reactions (Na(+)-K(+), Mg(2+)-K(+), and Ca(2+)-K(+)) occurred in these salt solutions than in water (H(+)-K(+)). The ion exchange reactions affected bump, bulge, and crack formation on the biotite basal plane, as well as the release of biotite framework ions. In these salt solutions, numerous illite fibers precipitated after reaction for only 3 h at 95 °C. Interestingly, in slow illite precipitation processes, oriented aggregation of hexagonal nanoparticles forming the fibrous illite was observed. These results provide new information for understanding scCO(2)-brine-mica interactions in saline aquifers with different brine cation compositions, which can be useful for GCS as well as other subsurface projects.

Supercritical CO2–brine induced dissolution, swelling, and secondary mineral formation on phlogopite surfaces at 75–95 °C and 75 atm

To safely implement geologic carbon sequestration (GCS), a better understanding of geochemical reactions at supercritical CO2 (scCO2)–brine–clay mineral interfaces is necessary. This work investigated phlogopite dissolution and secondary mineral formation after freshly cleaved (001) surfaces were exposed to scCO2–brine systems. Phlogopite was used as a model clay mineral, and scCO2–1 M NaCl–phlogopite systems at 75 °C and 75 atm were chosen to mimic CO2 storage conditions in deep saline aquifers. Additional experiments were also performed at 95 °C to explore the effect of temperature on phlogopite dissolution. The dissolution activation energies for each element were calculated to be 64.2 kJ mol−1 for Si, 53.6 kJ mol−1 for Mg, and 78.4 kJ mol−1 for Al. Over 43 h of reaction time, the activation energy for K dissolution was calculated to be 35.9 kJ mol−1. A whole-mineral activation energy for phlogopite, 62.5 kJ mol−1, was estimated from the weighted mean values of the activation energies of the framework elements (Al, Si, and Mg). Swelling of the phlogopite outer layers, dissolution pit formation, and precipitation of both illite and amorphous silica were dominant at both temperatures. At 75 °C, normalized volumetric surface coverage (μm3/μm2) was 0.34 ± 0.74 for illite and 0.05 ± 0.90 for amorphous silica nanoparticles.

Biotite dissolution in brine at varied temperatures and CO2 pressures: its activation energy and potential CO2 intercalation.

For sustainable geologic CO(2) sequestration (GCS), it is important to understand the effects of temperature and CO(2) pressure on micas dissolution and surface morphological changes under saline hydrothermal conditions. Batch experiments were conducted with biotite (Fe-end member mica) under conditions relevant to GCS sites (35-95 °C and 75-120 atm CO(2)), and 1 M NaCl solution was used to mimic the brine. With increasing temperature, a transition from incongruent to congruent dissolution of biotite was observed. The dissolution activation energy based on Si release was calculated to be 52 ± 5 kJ mol(-1). By comparison with N(2) experiments, we showed that CO(2) injection greatly enhanced biotites dissolution and its surface morphology evolutions, such as crack formation and detachment of newly formed fibrous illite. For biotites dissolution and morphological evolutions, the pH effects of CO(2) were differentiated from the effects of bicarbonate complexation and CO(2) intercalation. Bicarbonate complexation effects on ion release from biotite were found to be minor under our experimental conditions. On the other hand, the CO(2) molecules in brine could get into the biotite interlayer and cause enhanced swelling of the biotite interlayer and hence the observed promotion of biotite surface cracking. The cracking created more reactive surface area in contact with brine and thus enhanced the later ion release from biotite. These results provide new information for understanding CO(2)-brine-mica interactions in saline aquifers with varied temperatures and CO(2) pressures, which can be useful for GCS site selection and operations.