Investigation of the complexation of metal-ions by strong ligands in fresh and marine water

SCOPE: The detection and investigation of metal ions bound in strong complexes in natural waters is a difficult task, due to low concentration of the metal ions themselves, and also of the strong ligands, which, moreover, are often not of a well-defined composition. Here, a method is proposed for the investigation of the speciation of metal ions in natural waters. OBJECTIVE AND METHOD: It is based on the sorption of metal ions on strongly sorbing ion exchange resins, i.e. complexing resins. For this reason the method is called Resin Titration. It has been shown in previous investigations that the concentration of metal ion totally sorbed by a particular resin, and its reaction coefficient in the solution phase in the presence of the resin, can be determined from the sorption data using a simple relationship. Here, a data treatment (the Ruzic linearization method) is proposed for also determining the concentration of the ligands responsible for the complex in equilibrium with the resin. RESULTS: The method was applied to data obtained by Resin Titration of a freshwater and a seawater. Copper(II) and aluminium(III) were considered, using Chelex 100 as a titrant, due to its strong sorbing properties towards these metal ions. The results were: the total metal concentration in equilibrium with the resin, the side reaction coefficients, and the concentration of ligands. In all these cases the ligands forming very strong complexes were found to be at concentration lower than that of the metals. CONCLUSION: The Ruzic linearization method allows the determination of the concentration of the ligands forming very strong complexes in equilibrium with Chelex 100. The reaction coefficient was better determined by the calculation method previously proposed for RT. The ligands responsible for the strong complexes were found to be at low concentration, often lower than that of the metal ions considered. The metal in the original sample is partly bound to these ligands, since the complexes are very strong. Only a part of the metal is linked to weaker ligands, or free.     

Sparse PCA and investigation of multi-elements compositional repositories: theory and applications

The geochemistry of floodplain sediments is fundamental to monitor environmental changes and to quantify their contribution to natural and anthropic processes. A floodplain sediment composition is a vector of positive elements which sum to a fixed constant. The analysis of high-dimensional compositions requires methods that produce results involving only a small portion of the original variables. On the other hand, the analysis must take into account the additional constraints specific to compositions. With the purpose of studying these problems, a new procedure for sparse PCA is proposed on European floodplain sediment samples.     

Obstetrical outcomes following amniocentesis performed after 24 weeks of gestation: A systematic review and meta-analysis

To evaluate obstetrical outcomes for women having late amniocentesis (on or after 24 weeks). Electronic databases were searched from inception to January 1st, 2023. The obstetrical outcomes evaluated were gestational age at delivery, preterm birth (PTB) < 37 weeks, PTB within 1 week from amniocentesis, premature prelabor rupture of membranes (pPROM), chorionamnionitis, placental abruption, intrauterine fetal demise (IUFD) and termination of pregnancy (TOP). The incidence of PTB <37 weeks was 4.85% (95% CI 3.48–6.56), while the incidence of PTB within 1 week was 1.42% (95% CI 0.66–2.45). The rate of pPROM was 2.85% (95% CI 1.21–3.32). The incidence of placental abruption was 0.91% (95% CI 0.16–2.25), while the rate of IUFD was 3.66% (95% CI 0.00–14.04). The rate of women who underwent TOP was 6.37% (95%CI 1.05–15.72). When comparing amniocentesis performed before or after 32 weeks, the incidence of PTB within 1 week was 1.48% (95% CI 0.42–3.19) and 2.38% (95% CI 0.40–5.95). Amniocentesis performed late after 24 weeks of gestation is an acceptable option for patients needing prenatal diagnosis in later gestation.     

Hydrochemical,isotopic and microbiota characterization of telese mineral waters (Southern Italy)

Environmental Geochemistry and Health - The study deals with the analyses of springs and wells at the base of Montepugliano Hill that represents the SE edge of the wide carbonate Matese massif...     

Particulate matter air pollution and respiratory impact on humans and animals

Air pollution is now fully acknowledged to be a public health problem and a social issue. Particulate matter (PM) concentration has been linked with several clinical manifestations of pulmonary and cardiovascular diseases and is associated with morbidity and mortality induced by respiratory diseases both in human and animals. Current research on airborne particle-induced health effects investigates the critical characteristics of particulate matter that determine their biological effects. Scientific evidence assessed that the size of the airborne particles and their surface area determine the potential to elicit inflammatory injury, oxidative damage, and other biological effects. Thus, the present review paper aims to summarize the current evidences and findings on the effect of air pollution on lung function in both humans and animals.     

Characterization of dissolved organic matter from saline soils by fluorescence spectroscopy

In this paper hydrophilic (HI) and hydrophobic (HO) fractions of dissolved organic matter (DOM) extracted from soils at different degrees of salinisation were characterised by means of fluorescence spectroscopy in the emission, excitation and synchronous-scan modes. Results provided evidence of the different chemical nature of DOM fractions and allowed to distinguish hydrophilic and hydrophobic fractions extracted from the same soil substrate. The strong decrease in fluorescence intensity observed with the increasing salinity of the soils can be utilised to obtain information on the salinity level of different soil substrates by comparison of spectral fluorescence intensities.     

Spatial variability of air pollutants in the city of Taranto, Italy and its potential impact on exposure assessment

Epidemiological studies typically use monitored air pollution data from a single station or as averaged data from several stations to estimate population exposure. In industrialized urban areas, this approach may present critical issues due to the spatial complexities of air pollutants which are emitted by different sources. This study focused on the city of Taranto, which is one of the most highly industrialized cities in southern Italy. Epidemiological studies have revealed several critical situations in this area, in terms of mortality excess and short-term health effects of air pollution. The aims of this paper are to study the variability of air pollutants in the city of Taranto and to interpret the results in relation to the applicability of the data in assessing population exposure. Meteorological and pollution data (SO2, NO2, PM10), measured simultaneously and continuously during the period 2006–2010 in five air quality stations, were analyzed. Relative and absolute spatial concentration variations were investigated by means of statistical indexes. Results show significant differences among stations. The highest correlation between stations was observed for PM10 concentrations, while critical values were found for NO2. The worst values were observed for the SO2 series. The high values of 90th percentile of differences between pairs of monitoring sites for the three pollutants index suggest that mean concentrations differ by large amounts from site to site. The overall analysis supports the hypothesis that various parts of the city are differently affected by the different emission sources, depending on meteorological conditions. In particular, analysis revealed that the influence of the industrial site may be primarily identified with the series of SO2 data which exhibit higher mean concentration values and positive correlations with wind intensity when the monitoring station is downwind from the industrial site. Results suggest evaluating the population exposure to air pollutants in industrialized cities by taking into account the possible zones of influence of different emission sources. More research is needed to identify an indicator, which ought to be a synthesis of several pollutants, and take into account the meteorological variables.     

The influence of diet on intra and inter-individual variability of urinary excretion of arsenic species in Italian healthy individuals

To study the effect of eating foods with a high arsenic (As) content on the intra and inter-individual variability of urinary concentrations of the As species, daily urine samples were collected for 10 consecutive days from 12 healthy male subjects. A daily food diary was kept throughout the study period. Personal exposure to airborne As was measured once during the study. As³, As⁵, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in all urine samples by inductive coupled plasma mass spectrometry, and the sum of As³ + As⁵ + MMA + DMA (iAs) by hydride generation-atomic absorption spectrophotometry. Exposure to airborne As was below the limit of detection in all samplings. As³ was found in only 19.2% and As⁵ in only 3.3% of the urine samples, whereas high urinary concentrations of arsenobetaine were observed. With the exception of arsenobetaine, expressed as a percentage, a significant inter-individual variability was observed for all species of As, for iAs and for the MMA/DMA ratio (p < 0.001). Instead, the intra-individual variability was significant only for the MMA/DMA ratio (p < 0.001). Among foods with a high As content, only a heavy consumption of seafood was shown to influence inter-individual variability of DMA%, arsenobetaine expressed as μg g⁻¹ creatinine and iAs. In conclusion, even in populations with a high intake of organic As through foods, the finding of a significant inter-individual but no significant intra-individual variability of urinary species confirms the usefulness of urinary As speciation for biological monitoring of exposure to As.     

Sunlight-induced degradation of soil-adsorbed veterinary antimicrobials Marbofloxacin and Enrofloxacin

Marbofloxacin (MAR) and Enrofloxacin (ENR), two largely employed veterinary Fluoroquinolones (FQs), were found to be present at the micrograms per kilogram level in agricultural soils of South Lombardy (Italy) several months after manuring. Distribution coefficients (K_d) from sorption experiments indicated a strong binding to the soil. Soil samples fortified with environmentally significant FQs amounts (0.5 mg kg⁻¹) were exposed to solar light that promoted extensive degradation (80%) of both drugs in 60-150 h. Thus, photochemistry could be considered a significant depollution path in the soil, although it was two orders of magnitudes slower than in aqueous solution and a fraction of the drug (ca. 20%) remained unaffected. For MAR the photoprocess was the same as in solution, and involved cleavage of the tetrahydrooxadiazine ring. On the contrary, with ENR only some of the photoproducts determined in water (those arising from a stepwise oxidation of the piperazine side chain) were observed. Substitution of the 6-fluoro by a hydroxyl group and reduction did not occur in the soil, supporting the previous contention that such processes required polar solvation of FQs. Consistently with this rationalization, the irradiation of thin layers of solid drugs led to essentially the same products distribution as in the soil. From the environmental point of view it is important to notice that photodegradation mainly affects the side-chains, while the fluoroquinolone ring, to which the biological effect is associated, is conserved up to the later stages of the degradation.     

Climate and conflicts: the security risks of global warming

Since the publication of the fourth assessment report of the Intergovernmental Panel on Climate Change in 2007, the securitization of global warming has reached a new level. Numerous public statements and a growing research literature have discussed the potential security risks and conflicts associated with climate change. This article provides an overview of this debate and introduces an assessment framework of climate stress, human security and societal impacts. Key fields of conflict will be addressed, including water stress, land use and food security, natural disasters and environmental migration. A few regional hot spots of climate security will be discussed, such as land-use conflicts in Northern Africa; floods, sea-level rise and human security in Southern Asia; glacier melting and water insecurity in Central Asia and Latin America; water conflicts in the Middle East; climate security in the Mediterranean; and the potential impact on rich countries. Finally, concepts and strategies will be considered to minimize the security risks and move from conflict to cooperation in climate policy.