A comprehensive investigation and assessment of mercury in intertidal sediment in continental coast of Shanghai

The aims of this paper were to survey the total Hg levels and distribution character in intertidal sediment in continental coast of Shanghai, and identify the environment factors that might influence the sediment Hg concentrations, and to assess the pollution degree and potential ecological risk of Hg in sediment. Eighty-eight surface sediment samples and 18 sediment cores were collected for Hg contamination analysis. Physicochemical properties including Eh, particle size, content of total organic carbon (TOC), and acid volatile sulfide (AVS) were also measured. Index of geo-accumulation (I _geo) and potential ecological risk index were used respectively to assess the pollution levels and the ecological risk of sediment Hg. The average of total Hg concentrations in surface sediments was 107.4?±?90.9 ng/g with the range from 0 to 465.9 ng/g. Higher Hg concentrations were generally found in surface sediments near sewage outfalls and the mouth of rivers. Total Hg concentrations were significantly correlated with TOC (p?<?0.05) both in surface (r?=?0.24) and core (r?=?0.29) sediments, but not with the other environment factors (Eh, AVS, and particle size). Geo-accumulation index indicated that Hg contamination in intertidal sediments was generally at none to moderate degree, while potential ecological risk index demonstrated that the risk caused by Hg were at moderate to considerable level. Intertidal sediment in continental coast of Shanghai has generally been contaminated by Hg, and it might pose moderate to considerable risk to the local ecosystem. The Hg contamination is related more to the coastal pollution sources and complicated hydrodynamic and sedimentary conditions than the other environment factors studied.     

Toxicity of tire wear particle leachate to the marine macroalga, Ulva lactuca

Tire wear particles filed from the treads of end-of-life vehicle tires have been added to sea water to examine the release of Zn and the toxicity of the resulting leachate and dilutions thereof to the marine macroalga, Ulva lactuca. Zinc release appeared to be diffusion-controlled, with a conditional rate constant of 5.4 μg[L(h)^1/2]⁻¹, and about 1.6% of total Zn was released after 120 h incubation. Exposure to increasing concentrations of leachate resulted in a non-linear reduction in the efficiency of photochemical energy conversion of U. lactuca and, with the exception of the undiluted leachate, increasing accumulation of Zn. Phototoxicity was significantly lower on exposure to equivalent concentrations of Zn added as Zn(NO₃)₂, suggesting that organic components of leachate are largely responsible for the overall toxicity to the alga. Given the ubiquity and abundance of TWP in urban coastal sediments, the generation, biogeochemistry and toxicity of tire leachate in the marine setting merit further attention.     

The impact of vegetation on sedimentary organic matter composition and PAH desorption

Relationships between sedimentary organic matter (SOM) composition and PAH desorption behavior were determined for vegetated and non-vegetated refinery distillate waste sediments. Sediments were fractionated into size, density, and humin fractions and analyzed for their organic matter content. Bulk sediment and humin fractions differed more in organic matter composition than size/density fractions. Vegetated humin and bulk sediments contained more polar organic carbon, black carbon, and modern (plant) carbon than non-vegetated sediment fractions. Desorption kinetics of phenanthrene, pyrene, chrysene, and C₃-phenanthrene/anthracenes from humin and bulk sediments were investigated using Tenax^® beads and a two-compartment, first-order kinetic model. PAH desorption from distillate waste sediments appeared to be controlled by the slow desorbing fractions of sediment; rate constants were similar to literature values for k_slow and k_{very slow}. After several decades of plant colonization and growth (Phragmites australis), vegetated sediment fractions more extensively desorbed PAHs and had faster desorption kinetics than non-vegetated sediment fractions.     

Theoretical and experimental investigations of mercury adsorption on hematite surfaces

One of the biggest environmental concerns caused by coal-fired power plants is the emission of mercury (Hg), which is toxic metal. To control the emission of Hg from coal-derived flue gas, it is important to understand the behavior and speciation of Hg as well as the interaction between Hg and solid materials in the flue gas stream. In this study, atomic-scale theoretical investigations using density functional theory (DFT) were carried out in conjunction with laboratory-scale experimental studies to investigate the adsorption behavior of Hg on hematite (α-Fe₂O₃). According to the DFT simulation, the adsorption energy calculation proposes that Hg physisorbs to the α-Fe₂O₃(0001) surface with an adsorption energy of ?0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens the Hg stability on the α-Fe₂O₃(0001) surface, as evidenced by a shortened Hg-surface equilibrium distance. The projected density of states (PDOS) analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing the adsorption strength. In summary, α-Fe₂O₃ has the ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl. For the laboratory-scale experiments, three types of α-Fe₂O₃ nanoparticles were prepared using the precursors Fe(NO₃)₃, Fe(ClO₄)₃, and FeCl₃, respectively. The particle shapes varied from diamond to irregular stepped and subrounded, and particle size ranged from 20 to 500 nm depending on the precursor used. The nanoparticles had the highest surface area (84.5 m²/g) due to their highly stepped surface morphology. Packed-bed reactor Hg exposure experiments resulted in this nanoparticles adsorbing more than 300 μg Hg/g. The Hg L_III-edge extended X-ray absorption fine structure spectroscopy also indicated that HgCl₂ physisorbed onto the α-Fe₂O₃ nanoparticles.

Implications: Atomic-scale theoretical simulations proposes that Hg physisorbs to the α-Fe₂O₃(0001) surface with an adsorption energy of ?0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens the Hg stability on the α-Fe₂O₃(0001) surface, as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing the adsorption strength. Following laboratory-scale experiment of Hg sorption also shows that HgCl₂ physisorbs onto α-Fe₂O₃ nanoparticles which have highly stepped structure.     

A laboratory-incubated redox oscillation experiment to investigate Hg fluxes from highly contaminated coastal marine sediments (Gulf of Trieste,Northern Adriatic Sea)

Mercury (Hg) mobility at the sediment–water interface was investigated during a laboratory incubation experiment conducted with highly contaminated sediments (13 μg g^-1) of the Gulf of Trieste. Undisturbed sediment was collected in front of the Isonzo River mouth, which inflows Hg-rich suspended material originating from the Idrija (NW Slovenia) mining district. Since hypoxic and anoxic conditions at the bottom are frequently observed and can influence the Hg biogeochemical behavior, a redox oscillation was simulated in the laboratory, at in situ temperature, using a dark flux chamber. Temporal variations of several parameters were monitored simultaneously: dissolved Hg (DHg) and methylmercury (MeHg), O₂, NH₄ ⁺, NO₃ ^- + NO₂ ^-, PO₄ ^3-, H₂S, dissolved Mn²⁺, dissolved inorganic and organic carbon (DIC and DOC). Under anoxic conditions, both Hg (665 ng m² day^-1) and MeHg (550 ng m² day^-1) fluxed from sediments into the water column, whereas re-oxygenation caused concentrations of MeHg and Hg to rapidly drop, probably due to re-adsorption onto Fe/Mn-oxyhydroxides and enhanced demethylation processes. Hence, during anoxic events, sediments of the Gulf of Trieste may be considered as an important source of DHg species for the water column. On the contrary, re-oxygenation of the bottom compartment mitigates Hg and MeHg release from the sediment, thus acting as a natural “defence” from possible interaction between the metal and the aquatic organisms.     

Toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 to the nematode Caenorhabditis elegans

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al₂O₃ and TiO₂ were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC₅₀) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC₅₀ for ZnO NPs (2.3 mg L⁻¹) and bulk ZnO was not significantly different, but significantly different between Al₂O₃ NPs (82 mg L⁻¹) and bulk Al₂O₃ (153 mg L⁻¹), and between TiO₂ NPs (80 mg L⁻¹) and bulk TiO₂ (136 mg L⁻¹). Oxide solubility influenced the toxicity of ZnO and Al₂O₃ NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.     

Perfluorinated compounds in Haihe River and Dagu Drainage Canal in Tianjin, China

In this study, nine perfluorinated compounds (PFCs) were investigated in water and sediment of Haihe River (HR) and Dagu Drainage Canal (DDC), Tianjin, China. The total PFCs in water samples from DDC (40-174 ng L⁻¹) was much greater than those from HR (12-74 ng L⁻¹). PFC contamination was severe at lower reaches of HR due to industry activities, while high PFCs were found in the middle of DDC due to the effluents from wastewater treatment plants. Perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were the predominant PFCs in aqueous phase. The total PFCs in sediments from DDC (1.6-7.7 ng g⁻¹ dry weight) were lower as compared to HR (7.1-16 ng g⁻¹), maybe due to the dredging of sediment in DDC conducted recently. PFOS was the major PFC in HR sediments followed by PFOA; while PFHxA was the major PFC in DDC sediments. Organic carbon calibrated sediment-water distribution coefficients (K_OC) were calculated for HR. The Log K_OC ranged from 3.3 to 4.4 for C7-C11 perfluorinated carboxylic acids, increasing by 0.1-0.6 log units with each additional CF₂ moiety. The log K_OC for 8:2 fluorotelomer unsaturated acid was reported for the first time with a mean value of 4.0. The log Koc of PFOS was higher than perfluoronanoic acid by 0.8 log units.     

Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques

Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg⁻¹. Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as μ-XRF, μ-XRD and μ-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 μm. The main Hg-species found in the soil samples were metacinnabar (β-HgS), cinnabar (α-HgS), corderoite (Hg₃S₂Cl₂), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 μm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution.     

Equilibrium partitioning theory to predict the sediment toxicity of the anionic surfactant C(12)-2-LAS to Corophium volutator

The study of the effect of the sorption of linear alkylbenzene sulfonates (LAS) on the bioavailability to marine benthic organisms is essential to refine the environmental risk assessment of these compounds. According to the equilibrium partitioning theory (EqP), the effect concentration in water-only exposure will be similar to the effect concentration in the sediment pore water. In this work, sorption and desorption experiments with two marine sediments were carried out using the compound C₁₂-2-LAS. The effect of the sediment sorption on the toxicity of benthic organisms was studied in water-only and in sediment bioassays with the marine mud shrimp Corophium volutator. In addition, three common spiking methods were tested for its application in the toxicity tests, as well as the stability of the surfactant during the water-only and sediment-water test duration. LC50 values obtained from water-only exposure showed a good correspondence with the pore water concentrations calculated from the sorption and desorption isotherms in the spiked sediments.     

In vivo genotoxicity assessment of titanium,zirconium and aluminium nanoparticles,and their microparticulated forms,in Drosophila

As in vivo system, we propose Drosophila melanogaster as a useful model for study the genotoxic risks associated with nanoparticle exposure. In this study we have carried out a genotoxic evaluation of titanium dioxide (TiO₂), zirconium oxide (ZrO₂) and aluminium oxide (Al₂O₃) nanoparticles and their microparticulated forms in D. melanogaster by using the wing somatic mutation and recombination assay. This assay is based on the principle that loss of heterozygosis and the corresponding expression of the suitable recessive markers, multiple wing hairs and flare-3, can lead to the formation of mutant clones in treated larvae, which are expressed as mutant spots on the wings of adult flies. Third instar larvae were feed with TiO₂, ZrO₂ and Al₂O₃ nanoparticles, and their microparticulated forms, at concentrations ranging from 0.1 to 10 mM. Although a certain level of aggregation/agglomeration was observed in solution, it must be noted than the constant digging activity of larvae ensures that treated medium pass constantly through the digestive tract ensuring exposure. The results showed that no significant increases in the frequency of all spots (e.g. small single, large single, twin, total mwh and total spots) were observed, indicating that these nanoparticles were not able to induce genotoxic activity in the wing spot assay of D. melanogaster. Negative data were also obtained with the microparticulated forms. This indicates that the nanoparticulated form of the selected nanomaterials does not modify the potential genotoxicity of their microparticulated versions. These in vivo results contribute to increase the genotoxicity database on the TiO₂, ZrO₂ and Al₂O₃ nanoparticles.     

Influence of sediment acidification on the bioaccumulation of metals in Ruditapes philippinarum

Background, aim and scope

The influence of pH (range 6.5–8.5) on the uptake of Zn, Cd, Pb, Cu, Ni, Cr, Hg, and As by juveniles of the clam Ruditapes philippinarum was examined in order to understand whether variation in sediment pH has significant repercussions on metal bioaccumulation.

Materials and methods

Clams were exposed to sediments collected in three locations in the Gulf of Cadiz (Huelva, Guadalquivir and Bay of Cadiz) and to contaminated particles derived from an accidental mining spill in Spain.

Results

With a notable exception of metal Cd, the concentration of metals within clams significantly increased (p?<?0.1) when sediment pH was lowered by one or two units. Moreover, the magnitude of this effect was dependent on the type of sediment contamination.

Discussion

Lower pH increases metal solubility and reduces or invert the metal sorption of metals to sediments. Increases in free metal ions in water favors metal uptake by clams, hence pH is an important factor controlling the mobility of these metals within sediments and their subsequent bioaccumulation within biota. Although sediment-water exchange of Cd can increase with acidification, this excess may be counterbalanced by the presence of ligands in seawater preventing the uptake by organism. Besides chlorines, Cd has also an affinity with carbonates and other ligands present in sea water. These Cd-carbonate complexes may reduce the bioavailable to organisms.

Conclusions

These results highlight the potential implications of sediment acidification, either due to the storage excess of organic matter or to the forced capture of CO₂, on the increasing metal availability to benthic organisms.

Recommendations and perspectives

This kind of studies should be increased to address the influence of acidification in the behavior, bioavailability, toxicity, and risk assessment of contaminants associated with sediments either above sub-seabed geological formations in marine environments or in high enriched by organic matter in estuarine areas. Recently, the capture of CO₂ in marine environments has been approved and started; it is necessary to address the potential impacts associated with leakages or other events occurring during the procedure of injection and storage of CO2.     

Arsenic and mercury bioaccumulation in the aquatic plant, Vallisneria neotropicalis

Arsenic (As) and mercury (Hg) are among the most toxic metals/metalloids. The overall goal of this study was to investigate the bioaccumulation of these trace elements in Vallisneria neotropicalis, a key trophic species in aquatic environments. For this purpose, As and Hg concentrations were determined in sediments and natural populations of V. neotropicalis in sub-estuaries of Mobile Bay (Alabama, USA), differing with respect to past and present anthropogenic impact. Analyses indicate that the Fish River is the most contaminated among the sub-estuaries investigated; levels of As found in Fish River sediments fall within a range that could potentially cause adverse effects in biota. Sediment As concentrations were only moderately correlated with those in V. neotropicalis; no correlation was found between sediment and plant Hg levels. However, several parameters could have masked such potential relationships (e.g., differences in sediment characteristics and “biological dilution” phenomena). Results presented herein highlight the numerous parameters that can influence metal/metalloids accumulation in aquatic plants as well as species-specific responses to trace element contamination. Finally, this study underscores the need for further investigation into contaminant bioaccumulation in ecologically and economically important coastal environments.     

Contrasting effects of black carbon amendments on PAH bioaccumulation by Chironomus plumosus larvae in two distinct sediments: role of water absorption and particle ingestion

Two sediment matrices with different characteristics were amended with chars from different sources for bioaccumulation assay with filter-feeding Chironomus plumosus larvae. Chars greatly decreased porewater concentrations of PAHs (C_iw) measured using polyethylene devices in sediments. In organic rich sediment matrix-based systems where suspended char particles were absent, PAH concentrations in larvae (C_iB) were significantly correlated with C_iw, and there was no difference in water-based bioaccumulation factors (BAFs) between different treatments, suggesting that water absorption was the main contaminant uptake route for larvae. In organic poor sediment matrix-based systems where suspended char particles were present, poor Pearson correlation between C_iB and C_iw was found, but there was a significant linear increase of BAF values with char contents, which indicated that ingestion of suspended char particles could also be important for PAH bioaccumulation. Therefore, we need to rethink of the effectiveness and risks for the application of black carbon to sediment/soil remediation.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Degradation of sulfonamides antibiotics in lake water and sediment

Degradation of three sulfonamides (SAs), namely sulfamethoxazole (SMX), sulfamethazine (SMZ), and sulfadimethoxine (SDM) in surface water and sediments collected from Taihu Lake and Dianchi Lake, China was investigated in this study. The surface water (5–10 cm) was collected from the east region of Taihu Lake, China. Two sets of degradation experiments were conducted in 3-L glass bottles containing 2 L of fresh lake water and 100 μg/L of individual SAs aerated by bubbling air at a rate of approximately 1.2 L/min, one of which was sterilized by the addition of NaN₃ (0.1 %). Sediment samples were taken from Taihu Lake and Dianchi Lake, China. For the sediment experiment, 5 g of sediment were weighed into a 50-mL glass tube, with 10 mg/kg of individual SAs. Different experimental conditions including the sediment types, sterilization, light exposure, and redox condition were also considered in the experiments. The three SAs degraded in lake water with half-lives (t _1/2) of 10.5–12.9 days, and the half-lives increased significantly to 31.9–49.8 days in the sterilized water. SMZ and SDM were degraded by abiotic processes in Taihu and Dianchi sediments, and the different experimental conditions and sediments characteristics had no significant effect on their declines. SMX, however, was mainly transformed by facultative anaerobes in Taihu and Dianchi sediments under anaerobic conditions, and the degradation rate of SMX in non-sterile sediment (t _1/2 of 9.6–16.7 days) were higher than in sterilized sediment (t _1/2 of 18.7–135.9 days). Under abiotic conditions, degradation of SMX in Dianchi sediment was faster than in Taihu sediment, probably due to the higher organic matter content and inorganic photosensitizers concentrations in Dianchi sediment. High initial SAs concentration inhibited the SAs degradation, which was likely related to the inhibition of microorganism activities by high SAs levels in sediments. Results from this study could provide information on the persistence of commonly used sulfanomides antibiotics in lake environment.     

Cutleaf coneflower (Rudbeckia laciniata L.) response to ozone and ethylenediurea (EDU)

Cutleaf coneflower (Rudbeckia laciniata L.) seedlings were placed into open-top chambers in May, 2004 and fumigated for 12 wks. Nine chambers were fumigated with either carbon-filtered air (CF), non-filtered air (NF) or twice-ambient (2×) ozone (O₃). Ethylenediurea (EDU) was applied as a foliar spray weekly at 0 (control), 200, 400 or 600 ppm. Foliar injury occurred at ambient (30%) and elevated O₃ (100%). Elevated O₃ resulted in significant decreases in biomass and nutritive quality. Ethylenediurea reduced percent of leaves injured, but decreased root and total biomass. Foliar concentrations of cell-wall constituents were not affected by EDU alone; however, EDU × O₃ interactions were observed for total cell-wall constituents and lignocellulose fraction. Our results demonstrated that O₃ altered the physiology and productivity of cutleaf coneflower, and although reducing visible injury EDU may be phytotoxic at higher concentrations.     

Effect of sediment properties on the sorption of C12-2-LAS in marine and estuarine sediments

Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment materials (pure clays and sea sand), with sediments treated to reduce their organic carbon content, and with field marine and estuarine sediments. C₁₂-2-LAS was used as a model compound. Sorption to the clays montmorillonite and kaolinite resulted in non-linear isotherms very similar for both clays. When reducing the organic content, sorption coefficients decreased proportionally to the fraction removed in fine grain sediments but this was not the case for the sandy sediment. The correlation of the sediment characteristics with the sorption coefficients at different surfactant concentrations showed that at concentrations below 10 μg C₁₂-2-LAS/L, the clay content correlated better with sorption, while the organic fraction became more significant at higher concentrations.     

北运河表层沉积物对重金属Cu、Pb、Zn的吸附

首先分析了北运河6个采样点表层沉积物中重金属含量及相关基本特征。通过实验室模拟实验,利用分配系数Kd评价沉积物对重金属Cu、Pb、Zn的吸附特性,进一步考察了水体pH变化和有机质对重金属在北运河沉积物上吸附的影响。结果表明,沉积物中重金属的含量顺序为Zn>Cu>Pb,去除有机质后,沉积物对重金属的吸附能力显著降低,但各采样点中的重金属含量,沉积物对重金属吸附能力,以及沉积物中的有机质含量并没有明显相关性,这可能是因为不同采样点中有机质种类与结构不同导致的。总之,北运河沉积物对Pb有很强的吸附能力,其次是Cu和Zn,而且,Cu、Zn、Pb的吸附量随着pH的升高逐渐增大,水体pH值对于Zn的吸附影响更大。     

An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications

The aqueous ozonolysis of α-pinene and β-pinene was conducted under simulated tropospheric conditions at different pHs and temperatures. Three kinds of products, peroxides, carbonyl compounds, and organic acids, were well characterized, and the detection of these products provides effective evidence for understanding the atmospheric aqueous reaction pathway. We have two interesting findings: (1) the unexpected formation of methacrolein (MACR), with a yield of ～40%, in the α-pinene–O₃ aqueous reaction indicates a potentially new SOA formation pathway, because MACR is one of the important precursors of SOA; and (2) the surprisingly high yields of H₂O₂, ～60% for the α-pinene–O₃ reaction and ～100% for the β-pinene–O₃ reaction, indicates that H₂O₂ can be a significant contributor to the origin and transformation of oxidants in the atmosphere, especially in the humid regions. Moreover, we have determined the rate constant for aqueous reaction between MACR and H₂O₂ in pH 2 to 7 and obtained its upper limit as 0.13 M L^?1 s^?1. A mechanism concerning the formation of the species mentioned above is proposed, and it differs from that in the gas-phase reaction. We suggest that water plays a key role in the mechanism, by participating in the reactions as a direct reactant and by removing the excess energy of intermediates formed in the reactions.     

Catalytic gasification of biomass (<Emphasis Type="Italic">Miscanthus</Emphasis>) enhanced by CO<Subscript>2</Subscript> sorption

The main objective of this work concerns the coupling of biomass gasification reaction and CO₂ sorption. The study shows the feasibility to promote biomass steam gasification in a dense fluidized bed reactor with CO₂ sorption to enhance tar removal and hydrogen production. It also proves the efficiency of CaO-Ca₁₂Al₁₄O₃₃/olivine bi-functional materials to reduce heavy tar production. Experiments have been carried out in a fluidized bed gasifier using steam as the fluidizing medium to improve hydrogen production. Bed materials consisting of CaO-based oxide for CO₂ sorption (CaO-Ca₁₂Al₁₄O₃₃) deposited on olivine for tar reduction were synthesized, their structural and textural properties were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and temperature-programmed reduction (TPR) methods, and the determination of their sorption capacity and stability analyzed by thermogravimetric analysis (TGA). It appears that this CaO-Ca₁₂Al₁₄O₃₃/olivine sorbent/catalyst presents a good CO₂ sorption stability (for seven cycles of carbonation/decarbonation). Compared to olivine and Fe/olivine in a fixed bed reactor for steam reforming of toluene chosen as tar model compound, it shows a better hydrogen production rate and a lower CO₂ selectivity due to its sorption on the CaO phase. In the biomass steam gasification, the use of CaO-Ca₁₂Al₁₄O₃₃/olivine as bed material at 700 °C leads to a higher H₂ production than olivine at 800 °C thanks to CO₂ sorption. Similar tar concentration and lighter tar production (analyzed by HPLC/UV) are observed. At 700 °C, sorbent addition allows to halve tar content and to eliminate the heaviest tars.