Chemical speciation of PM emissions from heavy-duty diesel vehicles equipped with diesel particulate filter (DPF) and selective catalytic reduction (SCR) retrofits

Four heavy-duty diesel vehicles (HDDVs) in six retrofitted configurations (CRT^®, V-SCRT^®, Z-SCRT^®, Horizon, DPX and CCRT^®) and a baseline vehicle operating without after--treatment were tested under cruise (50 mph), transient UDDS and idle driving modes. As a continuation of the work by Biswas et al. [Biswas, S., Hu, S., Verma, V., Herner, J., Robertson, W.J., Ayala, A., Sioutas, C., 2008. Physical properties of particulate matter (PM) from late model heavy-duty diesel vehicles operating with advanced emission control technologies. Atmospheric Environment 42, 5622–5634.] on particle physical parameters, this paper focuses on PM chemical characteristics (Total carbon [TC], Elemental carbon [EC], Organic Carbon [OC], ions and water-soluble organic carbon [WSOC]) for cruise and UDDS cycles only. Size-resolved PM collected by MOUDI–Nano-MOUDI was analyzed for TC, EC and OC and ions (such as sulfate, nitrate, ammonium, potassium, sodium and phosphate), while Teflon coated glass fiber filters from a high volume sampler were extracted to determine WSOC. The introduction of retrofits reduced PM mass emissions over 90% in cruise and 95% in UDDS. Similarly, significant reductions in the emission of major chemical constituents (TC, OC and EC) were achieved. Sulfate dominated PM composition in vehicle configurations (V-SCRT^®-UDDS, Z-SCRT^®-Cruise, CRT^® and DPX) with considerable nucleation mode and TC was predominant for configurations with less (Z-SCRT^®-UDDS) or insignificant (CCRT^®, Horizon) nucleation. The transient operation increases EC emissions, consistent with its higher accumulation PM mode content. In general, solubility of organic carbon is higher (average ～5 times) for retrofitted vehicles than the baseline vehicle. The retrofitted vehicles with catalyzed filters (DPX, CCRT^®) had decreased OC solubility (WSOC/OC: 8–25%) unlike those with uncatalyzed filters (SCRT^®s, Horizon; WSOC/OC ～ 60–100%). Ammonium was present predominantly in the nucleation mode, indicating that ternary nucleation may be the responsible mechanism for formation of these particles.     

Metals emitted from heavy-duty diesel vehicles equipped with advanced PM and NOX emission controls

Emission factors for elemental metals were determined from several heavy-duty diesel vehicles (HDDV) of 1998–2007 vintage, operating with advanced PM and/or NO_X emissions control retrofits on a heavy-duty chassis dynamometer, under steady state cruise, transient, and idle conditions. The emission control retrofits included diesel particulate filters (DPF): catalyzed and uncatalyzed, passive and active prototype vanadium- or zeolite-based selective catalytic reduction (SCR) systems, and a catalyzed DPF fitted on a hybrid diesel electric drive vehicle. The prototype SCR systems in combination with DPF retrofits are of particular interest because they represent the expected emissions controls for compliance with PM and NO_X regulations in 2010. PM samples from a full-exhaust dilution tunnel were collected on bulk filters, and on a Personal Cascade Impactor Sampler (PCIS) for total and water-soluble elemental analysis. All the DPFs significantly reduced emissions of total trace elements (>85% and >95% for cruise and for the Urban Dynamometer Driving Schedule (UDDS), respectively). However, we observed differences in the post-retrofit metals emissions due to driving cycle effects (i.e., exhaust temperature) and type of retrofit. In general, the metals emissions over cruise conditions (which leads to higher exhaust temperatures) were substantially different from the emissions over a transient cycle or while idling. For instance, during cruise, we observed higher levels of platinum (1.1 ± 0.6–4.2 ± 3.6 ng km^?1) for most of the retrofit-equipped vehicle tests compared to the baseline configuration (0.3 ± 0.1 ng km^?1). The vanadium-based DPF + SCR vehicle during cruise operation exhibited emissions of vanadium (562 ± 265 ng km^?1) and titanium (5841 ± 3050 ng km^?1), suggesting the possible release of actual SCR wash-coat (V₂O₅/TiO₂) from the catalyst under the higher temperatures characteristic of cruise operation. The vanadium emissions exhibited a bi-modal mass size distribution, with modes at <0.25 μm and 1.0–2.5 μm size ranges for the vanadium-based SCR system. For the DPF + SCR systems, a greater fraction of the metal emissions from the zeolite-based system is water-soluble compared to emissions from the vanadium-based system.     

Redox activity of urban quasi-ultrafine particles from primary and secondary sources

To characterize the redox activity profiles of atmospheric aerosols from primary (traffic) and secondary photochemical sources, ambient quasi-ultrafine particles were collected near downtown Los Angeles in two different time periods – morning (6:00–9:00 PDT) and afternoon (11:00–14:00 PDT) in the summer of 2008. Detailed chemical analysis of the collected samples, including water-soluble elements, inorganic ions, organic species and water soluble organic carbon (WSOC) was conducted and redox activity of the samples was measured by two different assays: the dithiothreitol (DTT) and the macrophage reactive oxygen species (ROS) assays. Tracers of secondary photochemical reactions, such as sulfate and organic acids were higher (2.1 ± 0.6 times for sulfate, and up to 3 times for the organic acids) in the afternoon period. WSOC was also elevated by 2.5 ± 0.9 times in the afternoon period due to photo-oxidation of primary particles during atmospheric aging. Redox activity measured by the DTT assay was considerably higher for the samples collected during the afternoon; on the other hand, diurnal trends in the ROS-based activity were not consistent between the morning and afternoon periods. A linear regression between redox activity and various PM chemical constituents showed that the DTT assay was highly correlated with WSOC (R² = 0.80), while ROS activity was associated mostly with water soluble transition metals (Vanadium, Nickel and Cadmium; R² > 0.70). The DTT and ROS assays, which are based on the generation of different oxidizing species by chemical PM constituents, provide important information for elucidating the health risks related to PM exposure from different sources. Thus, both primary and secondary particles possess high redox activity; however, photochemical transformations of primary emissions with atmospheric aging enhance the toxicological potency of primary particles in terms of generating oxidative stress and leading to subsequent damage in cells.     

Characterisation of particulate matter and gaseous emissions from a large ship diesel engine

Composition of exhaust from a ship diesel engine using heavy fuel oil (HFO) was investigated onboard a large cargo vessel. The emitted particulate matter (PM) properties related to environmental and health impacts were investigated along with composition of the gas-phase emissions. Mass, size distribution, chemical composition and microphysical structure of the PM were investigated. The emission factor for PM was 5.3 g (kg fuel)^?1. The mass size distribution showed a bimodal shape with two maxima: one in the accumulation mode with mean particle diameter D_P around 0.5 μm and one in the coarse mode at D_P around 7 μm. The PM composition was dominated by organic carbon (OC), ash and sulphate while the elemental carbon (EC) composed only a few percent of the total PM. Increase of the PM in exhaust upon cooling was associated with increase of OC and sulphate. Laser analysis of the adsorbed phase in the cooled exhaust showed presence of a rich mixture of polycyclic aromatic hydrocarbon (PAH) species with molecular mass 178–300 amu while PM collected in the hot exhaust showed only four PAH masses.Microstructure and elemental analysis of ship combustion residuals indicate three distinct morphological structures with different chemical composition: soot aggregates, significantly metal polluted; char particles, clean or containing minerals; mineral and/or ash particles. Additionally, organic carbon particles of unburned fuel or/and lubricating oil origin were observed. Hazardous constituents from the combustion of heavy fuel oil such as transitional and alkali earth metals (V, Ni, Ca, Fe) were observed in the PM samples.Measurements of gaseous composition in the exhaust of this particular ship showed emission factors that are on the low side of the interval of global emission factors published in literature for NO_x, hydrocarbons (HC) and CO.     

Source identification of personal exposure to fine particulate matter using organic tracers

Personal exposure to fine particulate matter (PM2.5) is due to both indoor and outdoor sources. Contributions of sources to personal exposure can be quite different from those observed at ambient sampling locations. The primary goal of this study was to investigate the effectiveness of using trace organic speciation data to help identify sources influencing PM2.5 exposure concentrations. Sixty-four 24-h PM2.5 samples were obtained on seven different subjects in and around Boulder, CO. The exposure samples were analyzed for PM2.5 mass, elemental and organic carbon, organic tracer compounds, water-soluble metals, ammonia, and nitrate. This study is the first to measure a broad distribution of organic tracer compounds in PM2.5 personal samples. PM2.5 mass exposure concentrations averaged 8.4 μg m^?3. Organic carbon was the dominant constituent of the PM2.5 mass. Forty-four organic species and 19 water-soluble metals were quantifiable in more than half of the samples. Fifty-four organic species and 16 water-soluble metals had measurement signal-to-noise ratios larger than two after blank subtraction.The dataset was analyzed by Principal Component Analysis (PCA) to determine the factors that account for the greatest variance. Eight significant factors were identified; each factor was matched to its likely source based primarily on the marker species that loaded the factor. The results were consistent with the expectation that multiple marker species for the same source loaded the same factor. Meat cooking was an important source of variability. The factor that represents meat cooking was highly correlated with organic carbon concentrations (r = 0.84). The correlation between ambient PM2.5 and PM2.5 exposure was relatively weak (r = 0.15). Time participants spent performing various activities was generally not well correlated with PCA factor scores, likely because activity duration does not measure emissions intensity. The PCA results demonstrate that organic tracers can aid in identifying factors that influence personal exposures to PM2.5.     

Effect of humate on biological treatment of wastewater containing heavy metals

This paper presents results of investigations on the influence of humic substances (humate, HS) on the biological treatment of wastewater containing heavy metals (Cr, Cu, Fe, Mn, Ni, and Zn). Respirometric studies indicated that the investigated system complied with the Haldane model for inhibitory wastes. Chemical analyses showed that, while the soluble COD removal was high (82%), only 7% of ammonia was oxidized to nitrate. An addition of HS (500 mg L⁻¹) mitigated the inhibitory effect of the wastewater on the returned activated sludge. The system with HS complied with the Monod model for non-inhibitory wastes, and the removal of ammonia and metals was 99% and over 90%, respectively. It is suggested that an application of HS could be beneficial for treatment plants receiving wastewater streams containing heavy metals.     

Emissions of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs from heavy-duty diesel vehicles with DPF and SCR

In total, 24 polycyclic aromatic hydrocarbons (PAHs) in both gas and particle phases and 35 nitro-PAHs in particle phase were analyzed in the exhaust from heavy-duty diesel vehicles equipped with after-treatment for particulate matter (PM) and NO_X control. The test vehicles were carried out using a chassis dynamometer under highway cruise, transient Urban Dynamometer Driving Schedule (UDDS), and idle operation. The after-treatment efficiently abated more than 90% of the total PAHs. Indeed, the particle-bound PAHs were reduced by >99%, and the gaseous PAHs were removed at various extents depending on the type of after-treatment and the test cycles. The PAHs in gas phase dominated the total PAH (gas + particle phases) emissions for all the test vehicles and for all cycles; that is, 99% of the two-ring and 98% of the three-ring and 97% of the four-ring and 95% of the carcinogenic PAHs were in the gas-phase after a diesel particle filter (DPF) and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must include this volatile fraction and cannot be based on the particle fraction only. The selective catalytic reduction (SCR) did not appear to promote nitration of the PAHs in general, although there might be some selective nitration of phenanthrene. Importantly the after-treatmtent reduced the equivalent B[a]P (B[a]Peq) emissions by >95%, suggesting a substantial health benefit.

Implications: This study demonstrated that after-treatments, including diesel particulate filters (DPF), diesel oxidation catalysts (DOC), and selective catalytic reduction (SCR), significantly reduce the emissions of PAHs from heavy-duty diesel engines. The gas-phase PAHs dominate the total PAH (gas + particle phases) emissions from heavy-duty diesel vehicles retrofitted with various DPFs and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must also include this volatile fraction and cannot be based on the particle fraction only.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Atmospheric concentrations and dry deposition fluxes of particulate trace metals in Salvador,Bahia, Brazil

Respiratory system is the major route of entry for airborne particulates, being the effect on the human organism dependent on chemical composition of the particles, exposure time and individual susceptibility. Airborne particulate trace metals are considered to represent a health hazard since they may be absorbed into human lung tissues during breathing. Fossil fuel and wood combustion, as well as waste incineration and industrial processes, are the main anthropic sources of metals to the atmosphere. In urban areas, vehicular emissions—and dust resuspension associated to road traffic—become the most important manmade source.This work investigated the atmospheric concentrations of TSP, PM₁₀ and elements such as iron, manganese, copper and zinc, from three different sites around Salvador Region (Bahia, Brazil), namely: (i) Lapa Bus Station, strongly impacted by heavy-duty diesel vehicles; (ii) Aratu harbor, impacted by an intense movement of goods, including metal ores and concentrates and near industrial centers and; (iii) Bananeira Village located on Maré Island, a non-vehicle-influenced site, with activities such as handcraft work and fishery, although placed near the port. Results have pointed out that TSP concentrations ranged between 16.9 (Bananeira) and 354.0 μg m⁻³ (Aratu#1), while for PM₁₀ they ranged between 30.9 and 393.0 μg m⁻³, both in the Lapa Bus Station. Iron was the major element in both Lapa Station and Aratu (#1 and #2), with average concentrations in the PM₁₀ samples of 148.9, 79.6 and 205.0 ng m⁻³, respectively. Zinc, on the other hand, was predominant in samples from Bananeira, with an average concentration of 145.0 ng m⁻³ in TSP samples, since no PM₁₀ sample was taken from this site. The main sources of iron in the Lapa Station and Aratu harbor were, respectively, soil resuspension by buses and discharge of solid granaries, as fertilizers and metal ores. On the other hand, zinc and copper in the bus station were mainly from anthropic contributions, probably heavy-duty vehicle ageing and wearing actions releasing off Zn from tires and Cu from brake linings. In the Aratu harbor, the high copper concentrations found were probably due to the port's activities, as discharges of copper concentrate on its terminal, although other sources could be possible, as burning of diesel fuel on ships and heavy oil in heaters. Finally, the Bananeira site has been presented as a different profile, since this remote site has shown zinc as the most abundant element, demonstrating to have an unexpected anthropic contribution. On a mass-to-mass basis, both zinc and manganese were in high levels in the Bananeira site and their presence strongly suggest the impact of other sources, such as the Industrial Center of Aratu and/or a siderurgy plant, not far away from that location.     

Size distribution and sources of trace metals and n-alkanes in the Athens urban aerosol during summer

Size-resolved, 24-h aerosol samples were collected from June–July 2001 by means of an Andersen high-volume cascade impactor. Sampling was conducted in a central avenue (Patission) characterised by heavy traffic, 21 m above street level, in the Athens city centre. Samples were analysed by atomic absorption spectrometry and gas chromatography to determine the size distribution of nine metallic elements (Cd, Pb, V, Ni, Mn, Cr, Cu, Fe, Al) and n-alkanes (with carbon numbers in the range 18–35). The aerosol mass median diameter (MMD) was calculated by means of probit analysis on the cumulative mass concentration size distribution for each metals and n-alkane. The total n-alkane mass concentration (TNA) in total suspended particles (TSP) ranged from 72 to 1506 ng m⁻³ while the total metal concentration ranged from 5.6 to 28.6 μg m⁻³. The results showed that metals such as Cd, V and Ni are characterised by a MMD <1 μm, while the MMD for Pb and Mn are ∼1 μm. Such metals are generally considered to have anthropogenic emission sources. Other metals such as Al, Fe, Cu and Cr were found to have MMD=2–6 μm, which generally originate from soil dust or mechanical abrasion processes. The Carbon number profile of n-alkane compounds showed a strong anthropogenic source with only a minor biogenic influence. The concentration of most n-alkanes was characterised by high variability during the sampling period, in contrast to the concentration of most trace metals. Most n-alkanes had a unimodal size distribution with MMD=1–2 μm similar to those of some trace metals (Pb, Mn), which originate mostly from vehicle emissions. This is a strong indication that these species have a common source. Finally, gas–particle partitioning of n-alkanes was also examined for different particle sizes by means of the relationship between the partition constant K_p and saturation vapour pressure (p_L⁰) as proposed by current sorption models.     

Evaluation of airborne particulate matter and metals data in personal,indoor and outdoor environments using ED-XRF and ICP-MS and co-located duplicate samples

Factors and sources affecting measurement uncertainty associated with monitoring metals in airborne particulate matter (PM) were investigated as part of the Windsor, Ontario Exposure Assessment Study (WOEAS). The assessment was made using co-located duplicate samples and a comparison of two analytical approaches: ED-XRF and ICP-MS. Sampling variability was estimated using relative percent difference (RPD) of co-located duplicate samples. The comparison of ICP-MS and ED-XRF results yields very good correlations (R² ≥ 0.7) for elements present at concentrations that pass both ICP-MS and ED-XRF detection limits (e.g. Fe, Mn, Zn, Pb and Cu). PM concentration ranges (median, sample number) of 24-h indoor PM₁₀ and personal PM₁₀ filters, and outdoor PM_2.5 filters were determined to be 2.2–40.7 (11.0, n = 48) μg m^?3, 8.0–48.3 (11.9, n = 48) μg m^?3, and 17.1–42.3 (21.6, n = 18) μg m^?3, respectively. The gravimetric analytical results reveal that the variations in PM mass measurements for same-day sampling are insignificant compared to temporal or spatial variations: 92%, 100% and 96% of indoor, outdoor and personal duplicate samples, respectively, pass the quality criteria (RPD ≤ 20%). Uncertainties associated with ED-XRF elemental measurements of S, Ca, Mn, Fe and Zn for 24-h filter samples are low: 78%–100% of the duplicate samples passed the quality criteria. In the case of 24-h filter samples using ICP-MS, more elements passed the quality criteria due to the lower detection limits. These were: Li, Na, K, Ca, Si, Al, V, Fe, Mn, Co, Cu, Mo, Ag, Zn, Pb, As, Mg, Sb, Sn, Sr, Th, Ti, Tl, and U. Low air concentrations of metals (near or below instrumental detection limits) and/or inadvertent introduction of metal contamination are the main causes for excluding elements based on the pass/fail criteria. Uncertainty associated with elemental measurements must be assessed on an element-by-element basis.     

Input-export fluxes of heavy metals in the Cochin estuary,southwest coast of India

Cochin estuary (CE) is one of the largest tropical estuaries along the southwest coast of India, sustaining rich bio-resources. Several studies enlighten the environmental changes in the CE caused by anthropogenic activities. In the present study, an attempt has been made to quantify the heavy metal (dissolved and particulate) fluxes brought by the six rivers into the CE with their exchange into the coastal ocean through the major inlet at Cochin during a steady flow period (October–November 2015). The water flux across the inlet was quantified using an acoustic doppler current profiler. The measured daily input of dissolved metals from the rivers was 2.43?×?10³ kg Fe, 334 kg Zn, 259 kg Ni, and 83 kg Cr, while that of particulate metals were 85.30?×?10³ kg Fe, 8. 6?×?10³ kg Mn, 236.9 kg Cr, and 111.9 kg Zn. The net export of metals through the Cochin inlet (per tidal cycle) was 3.3?×?10³ kg Fe, 515 kg Cr, 150 kg Zn, and 5 kg Ni in dissolved form and 3.32?×?10⁵ kg Fe, 1747 kg Mn, 1636 kg Cr, 1397 kg Zn, and 586 kg Ni in particulate form. The high concentrations of metals during ebb tides are clear indications of their contribution from the industrial conglomerates (industrial units of metallurgy, catalyst, fertilizer, and pesticides) located in the Periyar River. The significance of this study is that the export fluxes may increase further during the summer monsoon (June to September), which may impact the abundant fishery emanating in the coastal environment during the period due to intense upwelling.

     

Phytoremedial assessment of flora tolerant to heavy metals in the contaminated soils of an abandoned Pb mine in Central Portugal

Significant accumulation of heavy metals in soils and flora exists around the abandoned Barbadalhos Pb mine in Central Portugal. Soil and plant samples [49 species] were collected from two line transects, LT 1 and LT 2, in the mineralized and non-mineralized area, respectively to gain a comprehensive picture of heavy metals in soils and flora to assess its potential for phytoremediation. Phytosociological inventories of the vegetation were made using the Braun-Blanquet cover-abundance scale. Metal concentrations in soil ranged from (in mg kg^?1): 98–9330 [Pb], 110–517 [Zn], 7.1–50 [Co], 69–123 [Cr], 31–193 [Cu], 33 400–98 500 [Fe], 7.7–51 [Ni], 0.95–13 [Ag], 2.8–208 [As], and 71–2220 [Mn] along LT 1; and 24–93 [Pb], 30–162 [Zn], 3.7–34 [Co], 61–196 [Cr], 21–46 [Cu], 24 100–59 400 [Fe], 17–87 [Ni], 0.71–1.9 [Ag], 4.3–12 [As], and 44–1800 [Mn] along LT 2. Plant metal content ranged from (in mg kg^?1): 1.11–548 [Pb], 7.06–1020 [Zn], 0.08–2.09 [Co], 0.09–2.03 [Cr], 2.63–38.5 [Cu], 10.4–4450 [Fe], 0.38–8.9 [Ni], and 0.03–1.9 [Ag] along LT 1; and 0.94–11.58 [Pb], 2.83–96.5 [Zn], 0.12–1.44 [Co], 0.21–1.49 [Cr], 1.61–22.7 [Cu], 4.6–2050 [Fe], 0.51–4.81 [Ni], and 0.02–0.31 [Ag] along LT 2. Plants with highest uptake of metals were: Cistus salvifolius (548 mg Pb kg^?1), Digitalis purpurea (1017 mg Zn kg^?1 and 4450 mg Fe kg^?1). Mentha suavolens and Ruscus ulmifolius were seen to hyperaccumulate Ag (1.9 and 1 mg Ag kg^?1, respectively). More metals and higher concentrations were traced in plants from LT 1, especially for Pb and Zn.     

Size and composition distributions of particulate matter emissions: part 2--heavy-duty diesel vehicles

Particulate matter (PM) emissions from heavy-duty diesel vehicles (HDDVs) were collected using a chassis dynamometer/dilution sampling system that employed filter-based samplers, cascade impactors, and scanning mobility particle size (SMPS) measurements. Four diesel vehicles with different engine and emission control technologies were tested using the California Air Resources Board Heavy Heavy-Duty Diesel Truck (HHDDT) 5 mode driving cycle. Vehicles were tested using a simulated inertial weight of either 56,000 or 66,000 lb. Exhaust particles were then analyzed for total carbon, elemental carbon (EC), organic matter (OM), and water-soluble ions. HDDV fine (< or =1.8 microm aerodynamic diameter; PM1.8) and ultrafine (0.056-0.1 microm aerodynamic diameter; PM0.1) PM emission rates ranged from 181-581 mg/km and 25-72 mg/km, respectively, with the highest emission rates in both size fractions associated with the oldest vehicle tested. Older diesel vehicles produced fine and ultrafine exhaust particles with higher EC/OM ratios than newer vehicles. Transient modes produced very high EC/OM ratios whereas idle and creep modes produced very low EC/OM ratios. Calcium was the most abundant water-soluble ion with smaller amounts of magnesium, sodium, ammonium ion, and sulfate also detected. Particle mass distributions emitted during the full 5-mode HDDV tests peaked between 100-180 nm and their shapes were not a function of vehicle age. In contrast, particle mass distributions emitted during the idle and creep driving modes from the newest diesel vehicle had a peak diameter of approximately 70 nm, whereas mass distributions emitted from older vehicles had a peak diameter larger than 100 nm for both the idle and creep modes. Increasing inertial loads reduced the OM emissions, causing the residual EC emissions to shift to smaller sizes. The same HDDV tested at 56,000 and 66,000 lb had higher PM0.1 EC emissions (+22%) and lower PM0.1 OM emissions (-38%) at the higher load condition.     

Particulate matter emissions from on-road vehicles in a freeway tunnel study

Particulate matter, including coarse particles (PM_2.5–10, aerodynamic diameter of particle between 2.5 and 10 μm) and fine particles (PM_2.5, aerodynamic diameter of particle lower than 2.5 μm) and their compositions, including elemental carbon, organic carbon, and 11 water-soluble ionic species, and elements, were measured in a tunnel study. A comparison of the six-hour average of light-duty vehicle (LDV) flow of the two sampling periods showed that the peak hours over the weekend were higher than those on weekdays. However, the flow of heavy-duty vehicles (HDVs) on the weekdays was significant higher than that during the weekend in this study. EC and OC content were 49% for PM_2.5–10 and 47% for PM_2.5 in the tunnel center. EC content was higher than OC content in PM_2.5–10, but EC was about 2.3 times OC for PM_2.5. Sulfate, nitrate, ammonium were the main species for PM_2.5–10 and PM_2.5. The element contents of Na, Al, Ca, Fe and K were over 0.8 μg m^?3 in PM_2.5–10 and PM_2.5. In addition, the concentrations of S, Ba, Pb, and Zn were higher than 0.1 μg m^?3 for PM_2.5–10 and PM_2.5. The emission factors of PM_2.5–10 and PM_2.5 were 18 ± 6.5 and 39 ± 11 mg km^?1-vehicle, respectively. The emission factors of EC/OC were 3.6/2.7 mg km^?1-vehicle for PM_2.5–10 and 15/4.7 mg km^?1-vehicle for PM_2.5 Furthermore, the emission factors of water-soluble ions were 0.028(Mg²⁺)–0.81(SO₄^2?) and 0.027(NO₂^?)–0.97(SO₄^2?) mg km^?1-vehicle for PM_2.5–10 and PM_2.5, respectively. Elemental emission factors were 0.003(V)–1.6(Fe) and 0.001(Cd)–1.05(Na) mg km^?1-vehicle for PM_2.5–10 and PM_2.5, respectively.     

Adsorption of a dye on clay and sand. Use of cyclodextrins as solubility-enhancement agents

Laboratory-scale studies were aimed at elucidating the physico-chemical aspects on the removal process of crystal violet (CV) from waters and solid substrates. The laponite clay (RD) and sand were chosen for the double aim at investigating them as CV adsorbents for water treatment and as substrates which mime the soil components. Sand is very effective in removing CV from waters. The cyclodextrins (CDs) were exploited as solubility-enhancement agents to remove CV from the solid substrates. They are powerful solvent media because they extract the CV from sand forming water-soluble CV/CD inclusion complexes and do not show affinity for sand. Optimum performance was shown by the modified CDs (i.e. hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin). A linear correlation between the logarithm of the equilibrium constant for the CV/CD inclusion complexes formation (K_cpx) and the maximum amount of CV extracted from sand in the columns experiments at a flow rate of 1.5 ml min⁻¹ was drawn. This relationship predicts that CDs with K_cpx < 180 M⁻¹ are not suitable for CV removal from sand. CDs failed to displace CV from RD because they generate the formation of RD clusters where CV remains entrapped.     

Trace metals in soil and leaves of Jacaranda mimosifolia in Tshwane area,South Africa

Plant and soil have been identified as major sink of pollutants in the environment. We evaluated the reliability of biomonitoring of heavy metals in Tshwane area with the use of leaves of Jacaranda mimosifolia. The concentrations of heavy metals such as Ca, Mg, Fe, Pb, Zn, Cu, Sb were measured in leaves of J. mimosifolia and soils collected from 10 sites in the city of Tshwane during two sampling periods. The metals were analyzed with the use of ICP-MS. The result shows significant differences in the concentration of trace metals in all the sites (p < 0.01). The differences between the two sampling periods were statistically significant (p < 0.01). Concentration of metals from high traffic and industrial sites were significantly higher than in the residential areas (p < 0.01). Concentration factor suggests that translocation of metals from roots to leaves could be relevant only for some metals such as Ca, Mg and Sb. The study reveals an anthropogenic source for the trace metals. Leaves of J. mimosifolia were found to be a useful biomonitor of the determined trace metals.     

Metal mobilization in soil by two structurally defined polyphenols

Polyphenols including tannins comprise a large percentage of plant detritus such as leaf litter, and affect soil processes including metal dynamics. We tested the effects of tannins on soil metal mobilization by determining the binding stoichiometries of two model polyphenols to Al(III) and Fe(III) using micelle-mediated separation and inductively coupled plasma optical emission spectroscopy (ICP-OES). By fitting the data to the Langmuir model we found the higher molecular weight polyphenol (oenothein B) was able to bind more metal than the smaller polyphenol (epigallocatechin gallate, EGCg). For example, oenothein B bound 9.43 mol Fe mol^?1, while EGCg bound 4.41 mol of Fe mol^?1. Using the parameters from the binding model, we applied the Langmuir model for competitive binding to predict binding for mixtures of Al(III) and Fe(III). Using the parameters from the single metal experiments and information about polyphenol sorption to soils we built a model to predict metal mobilization from soils amended with polyphenols. We tested the model with three natural soils and found that it predicted mobilization of Fe and Al with r² = 0.92 and r² = 0.88, respectively. The amount of metal that was mobilized was directly proportional to the maximum amount of metal bound to the polyphenol. The secondary parameter in each model was the amount of weak organically chelated Fe or Al that was in the soil. This study provides the first compound-specific information about how natural polyphenols interact with metals in the environment. We propose a model that is applicable to developing phytochelation agents for metal detoxification, and we discuss how tannins may play a role in metal mobilization from soils.     

Mobilization of arsenic in aquifers from the Datong Basin,China: Evidence from geochemical and iron isotopic data

Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ⁵⁶Fe values of HCl-extracted poor-crystalline Fe(III) range widely from ?0.41‰ to 0.36‰. We interpret the low Fe(II)/Fe_Extractable ratios (<50%) and the negative correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/Fe_Extractable ratios (?70%) and positive correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ⁵⁶Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from ?0.01‰ to 0.24‰, which is consistent with the δ⁵⁶Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg^?1 and from 0.6 to 3.0 mg kg^?1, for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.     

Human health risk from organ-specific accumulation of toxic metals and response of antioxidants in edible fish species from Chenab River,Pakistan

In the current study, the bioaccumulation of essential and nonessential metals and related antioxidant activity were analyzed in three organs (muscle, gills, and liver) of herbivorous (HF) and carnivorous (CF) edible fish of Chenab River. The comparative analysis revealed a more heterogeneous accumulation of metals in the muscles of HF fish than that of CF fish [chromium (Cr, 3.4 μg g^?1), cobalt (Co, 1.7 μg g^?1), copper (Cu, 3 μg g^?1), and iron (Fe, 45 μg g^?1) versus Cr (1.3 μg g^?1), Co (0.1 μg g^?1), Cu (1.1 μg g^?1), and Fe (33 μg g^?1), respectively, P?<?0.001]. These results implied an organ-specific accumulation of metals at different trophic levels. According to logistic regression analysis, the bioaccumulation of metals had marked differences in HF and CF. The antioxidant activity was significantly related to the tissue type and the metals to which the organs are exposed to. The liver of CF fish had a higher activity of antioxidant superoxide dismutase (SOD), catalase (CAT), glutathione (GSH), and lipid peroxidase (LPO) than that of HF (P?<?0.05). LPO and guaiacol peroxidase (POD) in both groups were associated with a number of metals, but in HF, cadmium (Cd), Cr, Pb, and Zn were more related with the LPO and SOD activities. Moreover, Cd, Co, Fe, Pb, Ni, Cu, and Zn were above the permissible limits set by various agencies. In numerous cases, our results were even higher than those previously reported in the literature. The results provide an insight into the pollution pattern of Chenab River. These results may be helpful in the future to identify biomarkers of exposure in aquatic organisms.

State of mixture of atmospheric submicrometer black carbon particles and its effect on particulate light absorption

The state of mixture of light-absorbing carbonaceous particles was investigated in relation to light absorption properties using electron microscopic examinations, black carbon (BC) analyses of quartz filter by thermal/optical reflectance (TOR) method, measurements with two continuous light-absorbing photometers at a suburban site of Tsukuba, about 60 km northeast of Tokyo. The volume fraction of water-soluble material (?) in individual particles is important for assessing particulate light-absorbing and/or scattering of atmospheric aerosols. The values of ? in BC particles were evaluated by electron micrographs before and after dialysis (extraction) of water-soluble material. The mass absorption coefficient (MAC in units of m² g^?1) tended to increase with increasing the average ? in BC particles with the radius range of 0.05–0.5 μm. Thus, our results indicate that coatings of water-soluble material around BC particles can enhance the absorption of solar radiation. Moreover, the single scattering albedo (SSA) will increase because a large amount of coating material will scatter more light.