Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

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.     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

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.     

Effects of medium-pressure UV lamps radiation on water quality in a chlorinated indoor swimming pool

The aim of our study was to determine the impact of medium-pressure UV lamps radiation on water quality in a chlorinated indoor swimming pool. An indoor swimming pool was equipped with two medium-pressure UV lamps. We collected eight samples of water daily over a four-weeks period and measured total and free chlorine, pH, water temperature, bacteriological parameters, total organic carbon and trihalomethanes. During the first week, which served as control, medium-pressure UV lamps were turned off. During the next three weeks, medium-pressure UV lamps were kept on 24 h per day. The third week, we reduced the level of the injected chlorine into water, and the last week we also reduced the water renewal volume by 27%. Our results showed that bacteriological parameters remained within allowable french limits. When medium-pressure UV lamps were kept on, total, free and active chlorine levels were significantly increased (P<0.001), whereas combined chlorine level were significantly decreased (P<0.001 and P<0.05, respectively). The levels of chloroform and bromodichloromethane were significantly increased when medium-pressure UV lamps were kept on (P<0.001), whereas chlorodibromomethane and bromoform levels significantly decreased (P<0.05 and P<0.001, respectively). The additional formation of chloroform and bromodichloromethane may be explained by the increase in active chlorine and by radicalizing mechanisms initiated by UV radiation.     

Enantiomeric fractions and congener specific determination of polychlorinated biphenyls in eggs of predatory birds from Doñana National Park (Spain)

The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Do?ana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 microg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 microg/g f.w.) and booted eagle (0.10-1.5 microg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 microg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF not = 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values.     

Degradation of di-butyl-phthalate by soil bacteria

Twelve Gram-positive phthalate ester degraders were isolated from soil. Using Biolog GP2 plates, eight of them were identified as belonging to the Corynebacterium-Mycobacterium-Nocardia group, while the remaining four were unidentifiable. When cultured in the presence of di-butyl-phthalate (DBP) in basal salts solution, five of these isolates accomplished more than 90% of DBP degradation within 48 h (fast group), three were placed in the medium group, and the remaining four were placed in the slow group which caused less than 30% of DBP degradation within the same period of time. A 420 bp DNA fragment was amplified from six isolates and none of them fell within the slow group. When compared with the large subunit of phthalate dioxygenase gene (phtA) of Arthrobacter keyseri, 83% and 91% similarities were evident in the nucleotide and amino acid sequences, respectively. However, no correlation between cell surface hydrophobicity and phthalate degradation ability was evident. Six surfactants (Brij 30, Brij 35, Tergitoltype NP-10, Triton N-101, Triton X-100 and SDS) were tested for their abilities to increase degradation rate. When added at the critical micellar concentration (CMC), they all displayed strong growth inhibition against the three bacteria tested, with Brij 30 been the least toxic to isolates G2 and G11, and Brij 35 had the least inhibitory effect for G1. When half the CMC of Brij 30 was incorporated into the basal salts, the inhibitory effect on DBP degradation remained. Soil helped to minimize surfactant toxicity of surfactant and increase the degradation potential of some of the test bacteria. When DBP-amended soil had been aged for three months, decreases in bioavailability were observed but the effect varied tremendously between different organisms. For isolates G1, G2, G5, G7 and G17 the aging effects were almost non-exist. The present study indicates that selection of a suitable degrader may minimize the undesired effect of aging on bioremediation process.     

Prediction of ozone concentrations in Oporto city with statistical approaches

The performance of three statistical methods: time-series, multiple linear regression and feedforward artificial neural networks models were compared to predict the daily mean ozone concentrations. The study here reported was based on data from one urban site with traffic influences and one rural background site. The studies were performed for the year 2002 and the respective four trimesters separately. In the multiple linear regression and feedforward artificial neural network models, the concentrations of ozone, the concentrations of its precursors (nitrogen oxides) and some meteorological variables for one and two days before the prediction day were used as predictors. For the application of these models in the validation step, the inputs of ozone concentration for one and two days before were replaced by the ozone concentrations predicted by the models. The results showed that time-series modelling was not profitable. In the development step, similar performances were obtained with multiple linear regression and feedforward artificial neural network. Better performance indexes were achieved with feedforward artificial neural network models in validation step. Concluding, feedforward artificial neural network models were more efficient to predict ozone concentrations.     

Cadmium and zinc bioaccumulation and metallothionein response in two freshwater bivalves (Corbicula fluminea and Dreissena polymorpha) transplanted along a polymetallic gradient

This study was designed to compare the metallothionein (MT) response capacity of two freshwater bivalves, Corbicula fluminea and Dreissena polymorpha, along an environmental gradient of polymetallic pollution. The bivalves were transplanted into 4 stations in southwestern France, with a cadmium and zinc pollution gradient. MT and metal concentrations were measured in the soft bodies of the clams and mussels over 2.5 months. In the zebra mussels, variations in MT concentrations were strictly correlated to progressive Cd and Zn bioaccumulation. In contrast, the faster response in the clams appeared positively correlated to Cd accumulation only, with the activation of efficient detoxification mechanisms which limited Cd bioaccumulation and reduced Zn concentrations over time. Nevertheless, despite stronger metal accumulation factors in D. polymorpha, C. fluminea revealed higher sensitivity of MT response along the pollution gradient.