Practical applications of the fenton reaction to the removal of chlorinated aromatic pollutants

BACKGROUND: Chlorophenols (CPs) constitute a group of organic pollutants that are introduced into the environment as a result of several man-made activities, such as uncontrolled use of pesticides and herbicides, and as byproducts in the paper pulp bleaching. Promising removal technologies of chlorinated aromatics consist in the application of advanced oxidation processes (AOPs) that can provide an almost total degradation of a variety of contaminants. Among these, wide application find Fenton systems based on generation of reactive species having a high oxidizing power, such as hydroxyl radical HO*. Our objective was that of determining the overall degradation efficiency of the model compound 2,4-dichlorophenol (DCP) by thermal Fenton-type oxidation systems with a view toward defining in more details relevant process parameters, the effect of reaction temperature and of co-catalyst Cu2+. METHODS: Reaction conditions were similar to those generally adopted as optimal in many practical applications, i.e. pollutant/Fe2+ (as FeSO4) ratio ca. 20, Fe2+/Cu2+ (co-catalyst) 2:1, pH adjusted and controlled at pH 3, and H2O2 in excess (up to four-fold over the stoichiometric amount required for complete mineralization). RESULTS AND DISCUSSION: The results demonstrate that it is advantageous to carry out the reaction at a temperature markedly higher (70 degrees C) than ambient. The stepwise addition of H2O2 in aliquots yields an efficient transformation, while allowing a convenient control of the reaction exothermicity. Under these conditions, the essentially complete removal of the initial DCP is accomplished using just one equiv of H2O2 during 15 min; excess H2O2 (5 equivalents) yields extensive substrate mineralization. Also relevant, at 70 degrees C dechlorination of the initial DCP (and of derived reaction intermediates) is remarkably extensive (3-5% residual TOX), already with the addition of 1 equiv of H2O2. At the end of the reaction, IC and IC-MS analyses of the solution reveal that only low-molecular weight carboxylic acid (acetic, formic, oxalic, malonic, tartaric, etc.) contribute to the residual TOC. CONCLUSIONS: The whole of the results herein point to the advantage of performing the process at temperatures substantially higher than ambient (70 degrees C). Under the conditions adopted, almost complete degradation of the initial toxic compound can be achieved using hydrogen peroxide in fair excess (e.g., 3.5 equiv H2O2). RECOMMENDATIONS AND OUTLOOK: In applying practical Fenton-type degradation systems to heavily polluted wastes, either for the pre-treatment of waters with a high COD value prior to biodegradation or for complete mineralization of pollutants, the set up of appropriate reaction conditions appears to be a key factor. Also, it is desirable to keep the concentration of iron salts within the lower limits in order to minimize the production and disposal of iron oxide sludges.     

Survival and growth of bivalve larvae under heavy-metal stress

In a study of the toxicity of mercury, silver, copper, nickel, and zinc to larvae of the American oyster Crassostrea virginica and hard clam Mercenaria mercenaria, the concentrations at which 5% (LC₅), 50% (LC₅₀), and 95% (LC₉₅) of the larvae died were determined, as well as growth at the LC₅ and LC₅₀ values. The order of toxicity for oyster larvae was Hg>Ag>Cu>Ni, and for clam larvae Hg>Cu>Ag>Zn>Ni. Growth of larvae of both species, with the exception of clam larvae in nickel-treated water, was not reduced at the LC₅ values, but was markedly reduced at the LC₅₀ values.     

Sister chromatid exchanges in first-trimester chorionic villi after in vivo and in vitro exposure to diagnostic ultrasound

A study was done to evaluate the effects of diagnostic ultrasound on sister chromatid exchange (SCE) in first-trimester chorionic villi under controlled technical conditions. Chromosome analysis was performed by the direct method using spontaneous mitoses from the cytotrophoblast layer, and SCE visualization was accomplished by a 72 h treatment with 5-bromodeoxyuridine (BrdU) at a concentration of 10μg/ml. The slides were stained with ac ridine orange. Immediately before first-trimester chorionic villus sampling, a group of ten pregnant women was exposed to diagnostic ultrasound for 20min (in vivo exposure). This group of patients was compared with a control group who were not exposed. A mean value of SCE/cell frequency of 4·2 ± 0·2 was found in the exposed pregnancies, while a value of 3·7 ± 0·2 was observed in the control group. After in vitro exposure of chorionic villi obtained from elective abortions, the frequency of SCE/cell did not differ significantly among samples with different exposures (1,2, and 3 h) and controls. The positive control (mitomycin C) yielded a significant increase in SCE frequency.     

Prenatal diagnosis of congenital human cytomegalovirus infection

Fifteen fetuses at risk of congenital human cytomegalovirus (HCMV) infection underwent prenatal diagnosis at 16–30 weeks' gestation by a combination of amniocentesis and fetal blood sampling. HCMV was isolated from the amniotic fluid in six patients, but HCMV-specific IgM was detected in only three of them. Two of the nine neonates, who were delivered following a negative prenatal diagnosis, had congenital HCMV infection diagnosed by virus isolation in the urine. The interval from infection to prenatal testing was 3 and 4 weeks in the two false-negative cases and ⩾ 7 weeks in the true-positive cases. Although timely testing for HCMV infection allows the option of termination of pregnancy, it may be flawed by false-negative results.     

Amiodarone treatment in pregnancy for dilatative cardiomyopathy with ventricular malignant extrasystole and normal maternal and neonatal outcome

Amiodarone treatment in pregnancy might be difficult to handle because of the long half-life of the drug (14–28 days up to 2 months) and because it reduces maternal and neonatal thyroid activity. Although short-term use in pregnancy has been described in cases of fetal supraventricular tachycardia, there are few reports on the chronic use of the drug. In this paper we describe our experience with amiodarone treatment in two pregnant sisters with familial dilatative cardiomyopathy and ventricular malignant extrasystole. Prolonged administration of amiodarone (400–200 mg/die) since the beginning of pregnancy did not have any adverse effects; maternal and neonatal thyroid function was normal, as was the neurological and motor development of the neonates.     

Early prenatal sonographic diagnosis of neuropathic arthrogryposis multiplex congenita with osseous heterotopia

A prenatal diagnosis of arthrogryposis multiplex congenita (AMC) has been carried out on a 19-week-old fetus by means of echography. The ultrasonographic characteristics were unnatural position of the four limbs associated with articular anomalies together with absence of active fetal movements. A therapeutic interruption of pregnancy was performed and the diagnosis was confirmed. At autopsy, architectural disorder of the motor neurons of the anterior medullary horn revealed a neuropathic pathogenesis of the arthrogryposis. Moreover, at the lumbar level the spinal cord was progressively replaced by heterotopic bony tissue which caused a more severe deformity of the lower limbs compared with the upper. The aspects of anatomo-pathological, genetic, and differential diagnosis are discussed showing the precocity of the prenatal diagnosis and the peculiarity of the aetiology of our case.     

Fetal echocardiography using transvaginal and transabdominal probes during the first period of pregnancy: A comparative study

The authors compare the diagnostic possibilities of fetal transabdominal echocardiography versus transvaginal echocardiography. A larger diagnostic capacity is verified in different gestation ages with transvaginal probe between the 11th and 14th week of gestation. The results are emphasized by colour Doppler.     

Mapping lightning/human-caused wildfires occurrence under ignition point location uncertainty

Fire managers need to study fire history in terms of occurrence in order to understand and model the spatial distribution of the causes of ignition. Fire atlases are useful open sources of information, recording each single fire event by means of its geographical position. In such cases the fire event is considered as point-based, rather than area-based data, completely losing its surface nature. Thus, an accurate method is needed to estimate continuous density surfaces from ignition points where location is affected by a certain degree of uncertainty. Recently, the fire scientific community has focused its attention on the kernel density interpolation technique in order to convert point-based data into continuous surface or surface-data. The kernel density technique needs a priori setting of smoothing parameters, such as the bandwidth size. Up to now, the bandwidth size was often based on subjective choices still needing expert knowledge, eventually supported by empirical decisions, thus leading to serious uncertainties. Nonetheless, a geostatistical model able to describe the point concentration and consequently the clustering degree is required. This paper tries to solve such issues by implementing the kernel density adaptive mode. Lightning/human-caused fires occurrence was investigated in the region of Aragón's autonomy over 19 years (1983–2001) using 3428 and 4195 ignition points respectively for the two causes of fire origin. An analytical calibration procedure was implemented to select the most reliable density surfaces to reduce under/over-density estimation, overcoming the current drawbacks to define it by visual inspection or personal interpretation. Besides, ignition point location uncertainty was investigated to check the sensitivity of the proposed model. The different concentration degree and the dissimilar spatial pattern of the two datasets, allow testing the proposed calibration methodology under several conditions. After having discovered the slight sensitivity of the model to the exact point position, the obtained density surfaces for the two causes were combined to discover hotspot areas and spatial patterns of the two causes. Evident differences in spatial location of the origin causes were noted and described. The general trend follows the geographical features and the human activity of the study areas. The proposed technique should be promising to support decision-making in wildfire prevention actions, because of the occurrence map can be used as a response variable in fire risk predicting models.