Elemental characterization of PM10, PM2.5 and PM1 in the town of Genoa (Italy)

The particulate matter (PM) concentration and composition, the PM10, PM2.5, PM1 fractions, were studied in the urban area of Genoa, a coastal town in the northwest of Italy. Two instruments, the continuous monitor TEOM and the sequential sampler PARTISOL, were operated almost continuously on the same site from July 2001 to September 2004. Samples collected by PARTISOL were weighted to obtain PM concentration and then analysed by PIXE (particle induced X-ray emission) and by ED-XRF (energy dispersion X-ray fluorescence), obtaining concentrations for elements from Na to Pb. Some of the filters used in the TEOM microbalance were analysed by ED-XRF to calculate Pb concentration values averaged over 7-30 d periods.     

HCHs and DDTs in sediment-dwelling animals from the Yangtze Estuary, China

HCHs and DDTs in sediment-dwelling animals including mollusks and crabs from the Yangtze Estuary were determined by GC-ECD. Levels of t-HCH were in the range of 1.2-5.5 ng g(-1) and averaged 3.5 ng g(-1) in mollusks, while t-DDT concentrations ranged from 26.0 to 68.8 ng g(-1), with a mean of 34.5 ng g(-1). In crabs t-HCH concentrations varied from 2.0 to 25.7 ng g(-1) and averaged 13.8 ng g(-1), whereas the concentrations of t-DDT were in the range of 1.5-24.8 ng g(-1) with a mean value of 5.9 ng g(-1). The HCHs and DDTs levels depend on geographical position and sources, showing the high levels at fresh water area in the estuary, such as XP, CM and LHK sites, and lower at brackish water area, such as FX site, and little difference between species. Results also indicate there was no significant relationship between t-HCH (t-DDT) concentrations and lipid contents both in mollusks and crabs because of non-equilibrium state under a specific estuarine dynamics; smaller individuals accumulated more HCHs and DDTs than larger individuals of mollusks at LHK site, showing different uptake rate for these pesticides; moreover, HCHs and DDTs levels were lower in female crab bodies than male crab bodies suggesting that the release of spawning. BSAFs (Biota- Sediment Accumulation Factors) from sediment-dwelling animals for HCHs and DDTs show a significant "one high with two low" and "one low with two high" effect in the Yangtze Estuary.     

Cadmium accumulation and its influence on lipid peroxidation and antioxidative system in an aquatic plant, Bacopa monnieri L

Bacopa monnieri L. plants exposed to 10, 50, 100 and 200 microM cadmium (Cd) for 48, 96 and 144 h were analysed with reference to the accumulation of metal and its influence on various enzymatic and non-enzymatic antioxidants, thiobarbituric acid reactive substances (TBARS), photosynthetic pigments and protein content. The accumulation of Cd was found to be increased in a concentration and duration dependent manner with more Cd being accumulated in the root. TBARS content of the treated roots and leaves increased with increase in Cd concentration and exposure periods, indicating the occurrence of oxidative stress. Induction in the activities of superoxide dismutase (SOD), ascorbate peroxidase (APX) and guiacol peroxidase (GPX) was recorded in metal treated roots and leaves of B. monnieri. In contrast, a significant reduction in catalase activity in Cd treated B. monnieri was observed. An increase was also noted in the levels of cysteine and non-protein thiol contents of the roots of B. monnieri followed by a decline. However, in leaves, cysteine and non-protein thiol contents were found to be enhanced at all the Cd concentrations and exposure periods. A significant reduction in the level of ascorbic acid was observed in a concentration and duration dependent manner. The total chlorophyll and protein content of B. monnieri decreased with increase in Cd concentration at all the exposure periods. Results suggest that toxic concentrations of Cd caused oxidative damage as evidenced by increased lipid peroxidation and decreased chlorophyll and protein contents. However, B. monnieri is able to combat metal induced oxidative injury involving a mechanism of activation of various enzymatic and non-enzymatic antioxidants.     

Optimizing the specific surface area of fly ash-based sorbents for flue gas desulfurization

High performance sorbents for flue gas desulfurization can be synthesized by hydration of coal fly ash, calcium sulfate, and calcium oxide. In general, higher desulfurization activity correlates with higher sorbent surface area. Consequently, a major aim in sorbent synthesis is to maximize the sorbent surface area by optimizing the hydration conditions. This work presents an integrated modeling and optimization approach to sorbent synthesis based on statistical experimental design and two artificial intelligence techniques: neural network and genetic algorithm. In the first step of the approach, the main and interactive effects of three hydration variables on sorbent surface area were evaluated using a full factorial design. The hydration variables of interest to this study were hydration time, amount of coal fly ash, and amount of calcium sulfate and the levels investigated were 4-32 h, 5-15 g, and 0-12 g, respectively. In the second step, a neural network was used to model the relationship between the three hydration variables and the sorbent surface area. A genetic algorithm was used in the last step to optimize the input space of the resulting neural network model. According to this integrated modeling and optimization approach, an optimum sorbent surface area of 62.2m(2)g(-1) could be obtained by mixing 13.1g of coal fly ash and 5.5 g of calcium sulfate in a hydration process containing 100ml of water and 5 g of calcium oxide for a fixed hydration time of 10 h.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

Isoprene emission from tropical trees in Okinawa Island, Japan

This study surveyed isoprene emission from 42 indigenous and exotic tropical trees in subtropic Okinawa, Japan. Of the 42 trees studied, 4 emitted isoprene at a rate in excess of 20 μg g⁻¹ h⁻¹, and 28 showed the rates of 1–10 μg g⁻¹ h⁻¹. The remainder emitted less than 1 μg g⁻¹ h⁻¹. The majority of trees in this study may therefore fall within the lower emitting species. However, species in Moraceae that is indigenous in Okinawa emitted isoprene at relatively higher rates with an average of 14.2 μg g⁻¹ h⁻¹. The highest emission rate of 107.1 μg g⁻¹ h⁻¹ for Ficus virgata yielded the area basis rate of 47.4 nmol m⁻² s⁻¹, which is almost equivalent to the rate of high emitting species. Furthermore, a linear relationship between light intensity and isoprene emission was noted with Ficus virgata up to 1700 μmol m⁻² s⁻¹. These findings may show the potential importance of subtropical areas as sources of isoprene to the atmosphere.     

Recovery of phosphates from wastewater using converter slag: Kinetics analysis of a completely mixed phosphorus crystallization process

A phosphorus crystallization process for recovering phosphates was developed using a completely mixed reactor and powdered converter slag as a seed crystal. This completely mixed phosphorus crystallization process achieved a stable and high phosphorus recovery: the average PO4-P removal efficiency during 200 d of operation was 87%, with a range of 70-98%. The apparent volume of the slag doubled due to crystal growth during the long-term phosphorus-removal experiments. The Ca2+ concentration, slag dosage, and temperature were found to govern the phosphorus recovery system for a given condition of pH and hydraulic retention time. The equations for the rate constant and reaction order were obtained by evaluating the model parameters. The model developed in this study was observed to successfully simulate the behavior of effluent PO4-P in a completely mixed phosphorus crystallization reactor over a wide variety of operating conditions of temperature, Ca2+ concentration, and influent PO4-P. Model investigations of design factors suggest that the completely mixed phosphorus crystallization process with influent PO4-P concentrations of less than 10 mg l(-1) could ensure effluent PO4-P concentrations of less than 0.5 and 1.0 mg l(-1) during summer and winter in Korea, respectively.     

Copper modulates non-enzymatic antioxidants in the freshwater fish Channa punctata (Bloch) exposed to deltamethrin

The assessment of the ecotoxicological risks caused by pesticides to ecosystems are based on data on the toxicity and effects of pesticide preparations to non-target organisms like fish. Deltamethrin is a widely used pesticide based on pyrethroids, which is reported to be extremely toxic to fish species. Modulatory effect of copper pre-exposure (10 ppb) on deltamethrin (0.75 microg l-1)-induced oxidative stress was investigated in freshwater fish Channa punctata (Bloch). Non-enzymatic antioxidants were studied as biomarkers of exposure to deltamethrin and possible protection afforded by copper pre-exposure. Glutathione levels were reduced significantly (P<0.05) in liver of copper-acclimatized deltamethrin-exposed group when compared with deltamethrin-exposed groups. The total thiol levels of copper-acclimatized deltamethrin-exposed group was significantly lowered (P<0.01) in liver when compared with deltamethrin-exposed group, while non-protein thiol levels recorded a significant (P<0.01) increase in liver of copper-acclimatized deltamethrin-exposed group when compared with deltamethrin-exposed group. The lipid peroxidation levels of copper-acclimatized deltamethrin-exposed groups were significantly lowered (P<0.01) in liver when compared with deltamethrin-exposed group. Deltamethrin is known to induce toxic responses by generating reactive oxygen species and to neutralize its toxic effect various non-enzymatic antioxidants were found to be modulated thus implicating their role as biomarkers in pollution control programmes.     

Modeling lead bioavailability and bioaccumulation by Lumbriculus variegatus using artificial particles. Potential use in chemical remediation processes

Artificial particles, specifically a diverse selection of chromatographical resins, have been recommended and used as a useful experimental model to predict the bioavailability and bioaccumulation of sediment-bound organic chemicals. In this work the same experimental model was adopted to investigate the bioavailability and bioaccumulation of lead by the freshwater oligochaete Lumbriculus variegatus. Particle-water partition coefficients were also determined. Sand particles and the anionic exchange resin promoted a similar uptake and bioaccumulation of lead. Instead, in the presence of the cationic exchanger the metal was not detected in the animals. For neutral particles, the uptake and accumulation depended on the chemistry of the functional groups at the active sites. In addition, a significant negative correlation was found between bioaccumulation and the particle-water partition coefficients. These studies may help to develop alternative methods for chemical remediation of lead-contaminated aquatic systems.     

Statistical evaluation of chronic toxicity data on aquatic organisms for the hazard identification: the chemicals toxicity distribution approach

Presently, in the Globally Harmonised System of Classification and Labelling of Chemicals the classification of substances for long-term effects to aquatic life is based on acute toxicity in combination with degradation and/or bioaccumulation potential. Recently an OECD Working Group was created to develop the classification scheme to accommodate chronic toxicity data related to aquatic organisms for assigning a chronic hazard category. This study focuses on a new approach for setting chronic toxicity cut-off values based on Chemicals Toxicity Distributions (CTDs). A CTD is obtained through statistical fitting of the data used by regulatory bodies for setting hazard-based classifications. The CTDs were made using the lowest aquatic NOEC value of each chemical. A review of different toxicological sources reporting acute aquatic toxicities was carried out. Initially, the data were arranged according to the specific source and distributions for key taxonomic groups (i.e. fishes, crustaceans and algae) were evaluated separately. In most cases, no significant departures from normality were observed. Thereafter, a compiled database containing >900 values was developed and the CTDs were constructed for each taxonomic group. Significant deviation from normality (P < 0.05) was observed in the fishes and crustaceans' CTDs. However, this deviation was apparently produced by the presence of only seven values with NOECs <1 x 10(-5) mg l(-1), while high correlation between the data and the normal scores (r-values>or= 0.989) indicated that the data were samples from normal distributions. From these observations, potential cut-off values would allow quantitative estimations of the percentage of chemicals falling into each specific category. This approach results in a simple classification hazard scheme where most chemicals are covered in one of the categories, allowing a clear distribution of the chemicals among three categories for chronic toxicity.