Chiu-Wen Chen

Assessment of toxicity of polycyclic aromatic hydrocarbons in sediments of Kaohsiung Harbor, Taiwan

Polycyclic aromatic hydrocarbon (PAH) contamination and toxicity levels in the surface sediments of Kaohsiung Harbor, Taiwan were evaluated using sediment quality guidelines (SQGs) and toxic equivalent factors. Eighty surface sediment samples were collected from twenty locations in Kaohsiung Harbor for PAH analysis using gas chromatography/mass spectrometry (GC/MS). Concentrations of total PAHs varies from 34.0 to 16,700 ng/g with a mean concentration of 1490±2689 ng/g. The spatial distribution of PAHs reveals that PAH concentration is relatively higher in the river mouth regions, especially in the Salt River mouth where it gradually diminishes toward the harbor region. Distributions of PAHs, during both the wet and dry seasons, show that PAHs are more easily disbursed in the receiving sea water thereby leading to a wider range of chemical distribution. Hence, most of the chemicals accumulate in the harbor water channel. Diagnostic ratios show that the possible source of PAHs in the southern industrial area of the harbor could be coal combustion while in the other zones it could be petroleum combustion and/or a mixed sources. The toxic equivalent concentrations (TEQ(carc)) of PAHs varied from 3.9 to 1970 ng TEQ/g. The higher total TEQ(carc) values were found in the southern industrial area of the harbor. As compared with US sediment quality guidelines, the observed levels of PAHs in the industrial zone exceeded the effects range low (ERL), which will eventually cause acute biological damage. Based on the analyses using the SQGs, surface sediments from Kaohsiung Harbor were moderately contaminated and most samples have a low probability of toxicity pollution, except for the Salt River mouth situated in the south Kaohsiung Harbor area. This area has a medium to high probability of toxicity pollution.

Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation

In the first phase of this study, the effectiveness of intrinsic bioremediation on the containment of petroleum hydrocarbons was evaluated at a gasoline spill site. Evidences of the occurrence of intrinsic bioremediation within the BTEX (benzene, toluene, ethylbenzene, and xylenes) plume included (1) decreased BTEX concentrations; (2) depletion of dissolved oxygen (DO), nitrate, and sulfate; (3) production of dissolved ferrous iron, methane, and CO2; (4) deceased pH and redox potential; and (5) increased methanogens, total heterotrophs, and total anaerobes, especially within the highly contaminated areas. In the second phase of this study, enhanced aerobic bioremediation process was applied at site to enhance the BTEX decay rates. Air was injected into the subsurface near the mid-plume area to biostimulate the naturally occurring microorganisms for BTEX biodegradation. Field results showed that enhanced bioremediation process caused the change of BTEX removal mechanisms from anaerobic biodegradation inside the plume to aerobic biodegradation. This variation could be confirmed by the following field observations inside the plume due to the enhanced aerobic bioremediation process: (1) increased in DO, CO2, redox potential, nitrate, and sulfate, (2) decreased in dissolved ferrous iron, sulfide, and methane, (3) increased total heterotrophs and decreased total anaerobes. Field results also showed that the percentage of total BTEX removal increased from 92% to 99%, and the calculated total BTEX first-order natural attenuation rates increased from 0.0092% to 0.0188% per day, respectively, after the application of enhanced bioremediation system from the spill area to the downgradient area (located approximately 300 m from the source area).

Vertical profile, contamination assessment, and source apportionment of heavy metals in sediment cores of Kaohsiung Harbor, Taiwan

Six sediment cores collected at the Kaohsiung Harbor of Taiwan were analyzed to evaluate their vertical profiles, enrichments, accumulations, and source apportionments of heavy metals. This was performed to investigate any potential ecological risks posed by heavy metals. Results indicated that the mean heavy metal content (mg kg-1) in the six sediment cores was as follows: Hg (0.4-6.4), Cd (<0.05-2.4), Cr (18-820), Cu (16-760), Pb (31-140), and Zn (76-1900). The patterns of heavy metal content in the sediment cores differed substantially among the four river mouths. However, the vertical profiles of metals were relatively stable, indicating that wastewater has the constant characteristics and has been discharged into the rivers for a long period of time. Results of pollution assessment of enrichment factor, geo-accumulation index, and pollution load index revealed that river mouths experience severe enrichment, strong accumulation, and high contamination from the primary heavy metals. It was not consistent in the assessment results of mean effect range median quotient, potential ecological risk index, and total toxic unit method. Potential ecological risks caused by Hg in the sediments at Canon River and Love River mouths on aquatic organisms were extremely high. The estimates derived from the receptor modeling of multiple linear regression of the absolute principal component scores indicated that the contributions of the composite heavy metals derived from the Canon River and the Love River on the potential toxicity and risks to the water environment of Kaohsiung Harbor were highest, followed by those derived from Salt River and Jen-Gen River.

Vertical profile, sources, and equivalent toxicity of polycyclic aromatic hydrocarbons in sediment cores from the river mouths of Kaohsiung Harbor, Taiwan

Six sediment cores collected at four contaminated river mouths and two harbor entrances in Kaohsiung Harbor (Taiwan) were analyzed to evaluate the sources and potential toxicity of polycyclic aromatic hydrocarbons (PAHs). PAHs presented the wide variations ranging from 369±656 to 33,772±14,378 ng g(-1) at the six sampling sites. The composition of PAHs presented a uniform profile reflecting the importance of atmospheric input from vehicle exhausts or coal combustion in the river mouths. PAHs diagnostic ratios indicated a stronger influence of coal combustion in the Salt River mouth and the prevalence of petroleum combustion and mixed sources in the other rivers and harbor entrances. PAHs toxicity assessment using the mean effect range-median quotient (m-ERM-q: 0.011-1.804), benzo[a]pyrene-toxicity equivalent (TEQ(carc): 22-2819 ng TEQ g(-1)), and dioxin-toxicity equivalent (TEQ(fish): 37-5129 pg TEQ g(-1)) identified the Salt River mouth near the industrial area of the harbor as the most affected area.

Removal of polycyclic aromatic hydrocarbons from sediments using sodium persulfate activated by temperature and nanoscale zero-valent iron

The oxidation of 16 polycyclic aromatic hydrocarbons (PAHs) compounds in sediments by sodium persulfate (Na2S2O8) simultaneously activated by temperature and nano zero-valent iron (nZVI) as the source of catalytic ferrous iron was investigated. The effect of various controlling factors, including S2O82− (0.017–170 g/L), nZVI (0.01–1 g/L), and temperature (50–70 °C) were performed. The efficiency to remove PAHs was 10.7–39.1% for unactivated persulfate. The treated sample had over 50% of the persulfate still remaining from an initial persulfate dose of 170 g/L, whereas less than 1% of the persulfate remained from an initial persulfate dose of 0.017, 0.17, and 1.7 g/L. Adequate persulfate (170 g/L) must be present because it is the source of the sulfate radicals responsible for the degradation of PAHs. Results indicated that increasing temperature and the addition of nZVI into a persulfate-slurry system could enhance the persulfate oxidation process. The best removal efficiency (90%) was achieved after 24 hr while adding nZVI (0.01 g/L) to persulfate (170 g/L) at temperature of 70 °C. The results suggested that nZVI assisted persulfate oxidation without elevating temperature may be a suitable and economic alternative for the ex situ treatment of PAH-contaminated sediments. Implications: Nano zero-valent iron (nZVI) has been successfully applied to transform/degrade contaminants in soils and water. Additionally, nZVI has been used as a catalyst to activate persulfate for the treatment of various contaminants. In this study, with the support of temperature, nZVI-persulfate oxidation system for treatment of PAH-contaminated sediments was improved significantly and the treated sediment could meet remediation goals.

Fe3O4 Magnetic Nanoparticles: Characterization and Performance Exemplified by the Degradation of Methylene Blue in the Presence of Persulfate

Abstract In this study, the oxidation of methylene blue (MB) over iron oxide magnetic nanoparticles (Fe3O4), which effectively activates persulfate anions (S2O82−) to form sulfate free radicals (SO4−•), was explored. In addition, the effect of the initial pH, sodium persulfate (Na2S2O8, PS) concentration, and Fe3O4 content on the decolorization of MB was investigated. The results revealed that the decolorization rate increased when the persulfate concentration increased from 0.03 to 0.12 g/L and the Fe3O4 content from 0.1 to 0.8 g/L. Therefore, the Fe3O4 nanoparticles enhanced the decolorization of MB. The catalyst was analyzed using cyclic voltammetry (CV), three-dimensional excitation-emission fluorescence matrix (EEFM) spectroscopy, and zeta potential measurements. The CV spectra indicated that a reversible redox reaction may explain the high catalytic activity of the catalyst. EEFM was used to evaluate the yield of a fresh Fe3O4 catalyst, and two peaks were observed at EX/EM wavelengths of 230/300 nm and 270/300 nm. Furthermore, the structure and surface morphology of the catalyst were characterized using X-ray diffraction (XRD) and environmental scanning electron microscopy (ESEM)-energy dispersive spectroscopy (EDS), respectively. The XRD result confirmed the existence of Fe3O4 in the catalyst. ESEM was used to determine the Fe3O4 particle size, indicating a high degree of nanoparticle dispersion.

Distribution and contamination status of chromium in surface sediments of northern Kaohsiung Harbor, Taiwan.

The distribution, enrichment, accumulation, and potential ecological risk of chromium (Cr) in the surface sediments of northern Kaohsiung Harbor, Taiwan, China were investigated. Sediment samples from ten locations located between the river mouths and harbor entrance of northern Kaohsiung Harbor were collected quarterly in 2011 and characterized for Cr, aluminum, water content, organic matter, total nitrogen, total phosphorous, total grease, and grain size. Results showed that the Cr concentrations varied from 27.0 to 361.9 mg/kg with an average of (113.5 +/- 87.0) mg/kg. High Cr concentration was observed near the Jen-Gen River mouth. The mean Cr concentration was high at 255.5 mg/kg, which was at least 2 to 7 times than that of other sites. This might imply significant Cr contribution from upstream receiving tanneries wastewater into the Jen-Gen River. The spatial distribution of Cr reveals relatively high in the river mouth region, especially in Jen-Gen River, and gradually diminishes toward the harbor entrance region. This indicates that the major sources of Cr pollution from upstream industrial and municipal wastewaters discharged along the river bank; and Cr may drift with sea current and be dispersed into open sea. Moreover, Cr concentrations correlated closely to the physical-chemical properties of the sediments, which suggested the influence of industrial and municipal wastewaters discharged from the neighboring industrial parks and river basins. Results from the enrichment factor and geo-accumulation index analyses imply that the Jen-Gen River sediments can be characterized as moderate enrichment and none to medium accumulation of Cr, respectively. However, results of potential ecological risk index indicate that the sediment has low ecological potential risk. The results can provide valuable information to developing future strategies for the management of river mouth and harbor.

Synthesis of magnetic biochar from bamboo biomass to activate persulfate for the removal of polycyclic aromatic hydrocarbons in marine sediments

This study developed a new and cost-effective method for the remediation of marine sediments contaminated with PAHs. Fe3O4 particles were synthesized as the active component, supported on bamboo biochar (BB) to form a composite catalyst (Fe3O4-BB). The effects of critical parameters, including the initial pH, sodium persulfate (PS) concentration, and dose of catalyst were investigated. The concentration of high-molecular-weight PAHs in sediments was much higher than that of low-molecular-weight PAHs; pyrene was an especially prominent marker of PAH contamination in sediments. Fe3O4-BB/PS exhibited a substantial improvement in PAH degradation efficiency (degradation rate: Fe3O4-BB/PS, 86%; PS, 14%) at a PS concentration of 1.7×10-5M, catalyst concentration of 3.33g/L, and pH of 3.0. The results of this study demonstrate that possible activation mechanisms include Fe2+-Fe3+ redox coupling and electron shuttling that mediates electron transfer of the BB oxygen functional groups, promoting the generation of SO4- in the Fe3O4-BB/PS system.

Distribution, enrichment, accumulation and potential ecological risks of mercury in the sediments of Kaohsiung Harbor, Taiwan

The distribution, enrichment, accumulation and potential ecological risks of mercury (Hg) in the surface sediments of Kaohsiung Harbor, Taiwan, were investigated. Sediment samples from 20 locations throughout Kaohsiung Harbor were collected quarterly from 2006 to 2011, and characterised for mercury, aluminium, water content, organic matter, total nitrogen, total phosphorous, total grease and grain size. The results showed that Hg concentrations varied from 0.06–6.73 mg kg−1 with an average of 0.54±0.71 mg kg−1. The spatial distribution of Hg reveals that the Hg concentration is relatively higher in the river mouth regions, especially at the Love River and Canon River mouths from where it gradually diminishes toward the harbour entrance region. The results from the enrichment factor and geo-accumulation index analyses reveal that the sediments near the Love River and Canon River mouths experience severe enrichment and strong accumulation of Hg that originates from upstream sources of pollution. The assessment of biological effects indicates that concentrations of 92.5% Hg found in the sediment are higher than effects range low, implying that the harbour sediments may cause an adverse impact on aquatic lives. The results of a potential ecological risk index indicate that the sediment has higher to serious levels of ecological potential risks.

Determination and assessment of phthalate esters content in sediments from Kaohsiung Harbor, Taiwan

Phthalate esters (PAEs) are known organic endocrine disruptors. The distribution of 10 PAEs in sediments of Kaohsiung Harbor of Taiwan was studied using organic solvents extraction and quantified by gas chromatography/mass spectrometry. The average concentration of total PAEs (ΣPAEs) in the sediment was 8713±11,454ng/g dw with di-(2-ethylhexyl) phthalate (DEHP) (3630ng/g-dw) and diisononyl phthalate (DiNP) (3497ng/g dw) being the major species, which constitutes of 41.7% and 40.1% of ΣPAEs. PAEs concentration was relatively high near the river mouths, especially in Love River mouth, and diminished toward the harbor. Based on the sediment quality guidelines developed from previous studies, several of the observed PAE levels exceeded the Maximum Contaminant Level, especially for DEHP and thus may cause adverse effect in aquatic organisms.