Characterization and distribution of mineral content in fine and coarse airborne particle fractions by neutron activation analysis∗

Nowadays, much attention is devoted to the study of toxic elements at trace and sub-trace levels in the investigation of particulate matter composition, especially in PM₁₀ and PM_2.5. Furthermore, it should be considered that the behavior knowledge is an other important task for understanding such species. Finally, the determination of particular elements with a few data in literature can assume relevant importance in industrial processes (Pd, Rh, Ir, etc. for catalytic pot, Sm, Ce, Eu, etc. for optical fibers and electronic process). In this article, we apply a nuclear technique, i.e. Instrumental Neutron Activation Analysis, for the study of metal composition in fine and coarse fractions. This nuclear technique allows the determination of about 25 elements: for some of them, this is the first determination in the ambient air of Rome. The investigation was performed in a reserved area in downtown Rome during a 15-day intensive campaign. The sampled filters were irradiated at the nuclear reactor Triga Mark II (ENEA-Casaccia Laboratories) at neutron flux of 2.6?×?10¹²?n?cm^?2?s^?1 for 32.55?h. The measurements of the γ-ray allow the qualitative and quantitative analysis. The element levels in fine and coarse fractions will be shown with the correlations among some elements being more interesting in the toxicological field: basically, the concentrations are very low.     

Cadmium (Cd) and zinc (Zn) accumulation by Thai rice varieties and health risk assessment in a Cd–Zn co-contaminated paddy field: Effect of soil amendments

Environmental Geochemistry and Health - Zinc mining and smelting activities result in cadmium (Cd) and zinc (Zn) contamination in rice grains, causing deleterious impacts on human health and local...     

Presence of Cd‐binding proteins in pre‐exposed and not pre‐exposed cadmium brine shrimp Artemia

The presence of metal binding proteins has been variously suggested as indicating involvement in uptake, storage, transport and elimination of toxic metals and in the routine metabolism of metals in mammals and a variety of marine invertebrates. This report describes results on the characterization of Cd‐BPs obtained from cadmium pre‐exposed and not pre‐exposed Anemia. The effect of pre‐exposure in the Cd‐binding protein induction in Artemia is discussed.     

Variations in the elemental compositions of plants,and computer‐aided sampling in ecosystems∗

To obtain comparable results of multi‐element analysis of plant materials by different laboratories, a harmonized sampling procedure for terrestrial and marine ecosystems is essential. The heterogeneous distribution of chemical elements in living organisms is influenced by different biological parameters. These parameters are mainly characterized by genetic predetermination, seasonal changes, edaphic and climatic conditions, and delocalization processes of chemical substances by metabolic activities.

The biological variations of the element content in plants were divided into 5 systematic levels, which are: 1. the plant species; 2. the population; 3. the stand (within an ecosystem); 4. the individual; and 5. the plant compartment. Each of these systematic levels can be related to: 1. genetic variabilities; 2. different climatic, edaphic and anthropogenic influences; 3. microclimatic or microedaphic conditions; 4. age of plants (stage of development), exposure to environmental influences (light, wind, pollution etc.), seasonal changes; and 5. transport and deposition of substances within the different plant compartments (organs, tissues, cells, organelles).

An expert system for random and systematic sampling for multi‐element analysis of environmental materials, such as plants, soils and precipitation is presented. After statistical division of the research area, the program provides advice for contamination‐free collection of environmental samples.     

Interrelation of Cd‐lon concentrations and the growth and activities of microorganisms in two growth media†

Partitioning of native or anthropogenic heavy metals in solid and solution phases of soil is a result of network of several physico‐chemical reactions. The attainment of equilibrium between two phases is also regulated by biochemical processes. For practical purposes, the bioavailability of metal present in soil is predominantly regulated by the soil solution phase which is in dynamic equilibrium with the solid phase. The results of a model laboratory and greenhouse growth experiments have been used to investigate the effect of Cd‐ion concentrations (either in soil solution or in nutrient solution) on the growth and activities of microorganisms. The soil solution has been simulated by preparing a suspension of soil with 0.1 M NaNO₃ (1: 2.5) equilibrated for two hours. Important conclusions are as follows:

Increase in Cd‐ion concentration in soil solution or in nutrient solution induces corresponding adverse effect on the growth and activities of microorganisms. Thus, it seems that Cd‐ion concentration is a more sensitive indicator for assessing the effect of metal pollution upon the growth and activities of soil microorganisms in comparison to total Cd contents.

During active microbial growth phase, a large part of the organically bound Cd was released in the soil solution which is largely bioavailable. This process is termed as mobilisation. There was momentary increase of Cd‐ion concentration in soil solution which intoxicated the growing organisms. After this stage, the Cd ions from the solution phase were removed by the newly formed solid phase (nonviable biomass) and were transformed in non‐available form. This process is termed as immobilisation.

The consequences and importance of these results for practical agriculture and in deciding the limits or guidelines on the maximum tolerable metal load in soils are discussed.     

Cadmium in the terrestrial environment: Impact of long‐range atmospheric transport∗

Cadmium is supplied to Southern Norway in considerable amounts by atmospheric transport from other areas of Europe. This has caused a very marked increase of Cd levels in the natural environment in this area. Evidence of the main source areas is inferred from air concentration studies coupled to trajectory analysis. The extent of contamination is indicated from deposition studies and investigations of Cd in peat cores and surface soils, including soil profile distributions. The Cd content of vascular plants is substantially higher in Southern Norway than in areas farther north and further transfer in terrestrial food chains is occurring and may eventually lead to increased human exposure.     

The metabolism and distribution of [14C‐phenyl]‐ethyl parathion in a tropical soil under field conditions

The persistence, distribution and metabolism of [^l4C‐phenyl]‐ethyl parathion applied to soil columns in an agricultural farm were investigated under tropical field conditions. Volatilization, soil microbial activity, moisture levels and pH were found to influence the persistence, distribution and metabolism of this pesticide in the soil. There was rapid distribution of the pesticide in the soil matrix with time resulting in high levels of bound residues which reduced the overall rate of disappearance of parathion residues from the soil. The soil was slightly acidic but the metabolites, paraoxon, p‐nitrophenol and p‐aminophenol were detected in the soil extracts 7 days after pesticide application. After 72 days, 43.7% of the applied pesticide remained in soil composed of 18.9% extractable and 24.8% bound residues. A mechanism for the metabolism of ethyl parathion in this soil is given.     

Cleanup by solid‐phase extraction and HPLC of organochlorine insecticides and PCBS in various nonfatty and fatty samples

An accurate, simple and cheap extraction and cleanup procedure for capillary GC analysis of organo‐chlorine insecticides (OCs) in vegetables (cabbage and carrots) at the ng/g level, and for soil at the μg/g level is presented. The cleanup is carried out on solid‐phase extraction (SPE) cartridges, filled with 500 mg silica, 1 g of deactivated Florisil (10% w/w water), and 100 mg of anhydrous sodium sulphate. Recoveries >90% are obtained. The cleanup of OCs in fatty samples on an HPLC LiChrosorb Si 100 column is evaluated for subsequent capillary GC analysis. Fractionation of OCs and Aroclor 1254 and 1260 on an HPLC Nucleosil 100 column appears to be satisfactory.     

Effects of cucl2 on UV‐mutagenesis and on DNA damage in a restriction fragment of E. Coli gpt∗

CuCl₂ does not cause Trp⁺ reversion in E. coli WP2. However, when the bacteria are exposed to CuCl₂ and UV‐irradiated, a greater than 3‐fold enhancement of mutagenesis (compared to UV alone) is seen at 30 μMCuCl₂, and significant enhancement is seen even at 3 μM. The mechanism for this comutagenic effect was studied using a restriction fragment of the E. coli gpt gene. Whereas UV or CuCl₂ alone caused few strand breaks, UV + CuCl₂ induced breaks at every site. This reaction was blocked by KI, a free radical scavenger. While UV alone induced alkali‐labile sites, UV+ CuCl₂ induced many more such sites and altered the sequence specificity. We suggest that at least some of the comutagenic effect might be due to hydroxyl radical formed via a Fenton reaction.     

Metabolites of sulfur‐containing derivatives of the fungicides pentachloronitrobenzene and hexachlorobenzene in mammals,separated by capillary gas chromatography and identified by negative and positive Cl mass spectrometry

Biotransformation products of sulfur‐containing derivatives of pentachloronitro‐benzene and hexachlorobenzene in mammals, such as thiophenols, thioanisoles, phenols, anisoles and chlorinated benzenes have been identified by mass spectrometry of negative and positive ions produced by chemical ionisation. The capillary gas chromatograms of extracts from excreta of rats after application of N‐acetyl‐S‐(pentachlorophenyI)‐D,L‐cysteine, as well as of rabbits after application of S,S'‐(tetrachloro‐p‐phenylene)‐L,L'‐dicysteine, are shown.     

Immobilising of Cd,Pb, and Zn contaminated arable soils close to a former Pb/Zn smelter: a field study in Austria over 5 years

Numerous smelter sites are surrounded by rural land. The entrance of non-essential metals such as lead or cadmium into the food chain is very likely as well as phytotoxicity effects of zinc. Finding a realistic solution for these large-scale contaminations was one aim of this study. Previous results from pot experiments showed a high potential for the reduction of metals entering the food chain via crops grown on smelter-contaminated soils from Arnoldstein, Austria, by the use of amendments for immobilisation. A further aim was to optimise a field experiment for overcoming the gap between pot and field experiments and to look for long-term efficiency of the treatments [lime (CA), red mud (RM), gravel sludge + red mud (GS + RM)]. Field experiment results were obtained for 5 years. Besides soil and soil pore water samples, the following harvests were yielded: spring barley (Hordeum distichon ssp. L.) (2004–2005), narrowleaf plantain (Plantago lanceolata L.) (2006–2007) and velvet grass (Holcus lanatus L.) (2007–2008). The long-term efficiency of GS + RM led us to conclude that their application seems to be a realistic and practical measure for extensively contaminated land, best in combination with metal excluding cultivars.     

Evaluation of linear alkylbenzenesulfonate (LAS) biodegradability in sediment by solid‐phase extraction and HPLC analysis

The linear alkylbenzenesulfonate (LAS) sorption on environmental sediments has been known long ago. Their high concentrations reflect the massive input of these chemicals from household and industrial uses. However few attempts were made to identify biodegradation metabolites of LAS in sediment. In this report, a method for the determination of these compounds in sediment samples by high‐performance liquid chromatography (HPLC) is described. The first step of our work was performed by solid‐phase extraction with octadecyl‐bonded silica (C18) mini‐columns and provided a suitable recovery of LAS (90 ± 5%) and most metabolites. Furthermore, laboratory investigations led to study the behaviour of LAS in sediment. The environmental samples used for this purpose were collected from a pond (named étang de Bolmon) located in the French Mediterranean coast. Our results were in agreement with an aerobic biodegradation process of LAS that occurred only with high values of sediment redox potential and needed the samples to be vigorously shaken to ensure adequate mixing and suspension of particulate material. In a stagnant sediment or under anaerobic conditions, LAS is not degraded. p‐Sulfophenylacetic acid and p‐sulfocinnamic acid were evidenced as predominant metabolites and were found not to be persistent.     

Pollution from polychlorodibenzo‐p‐dioxins and furans: The case of several foundry plants in the Lombardy region

In 1991 a co‐operation between Public Health Office (U.S.S.L.) n° 18 of Brescia and the Chemical Section Laboratories of U.S.S.L. n° 38 of Milan concerning the possible environmental impact of foundry industrial activities performing metallic scraps recovering, has been undertaken.

Soil and surfaces have been classified in conformity with the National Toxicological Consultative Commission (C.C.T.N.) recommendation dated 12/02/1988'; owing to the characteristics of the processed material, besides heavy metals, polychlorodibenzo‐p‐dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and polychlorobiphenyls (PCBs) have been looked for.

The particulate matter collected from the filters positioned over the arc furnaces in 14 foundry plants has been characterized and classified, according both to C.C.T.N.¹ and to the Interministerial Board regulation dated 27/07/1985 for the first application of the Republic President Decree Law (D.P.R.) n° 915/1982, concerning wastes classification, based, in this case, on these toxic chlorinated compounds concentrations. From the very beginning, high levels of PCDDs and PCDFs have been detected, corroborating the very few literature data from foundry plants². The results obtained on 14 different foundries allow us to draw already some information, acceptable from the point of view of the statistical validity, about the pollution produced by this industry.     

Analysis of Cd,Cu, Pb,Zn, Hg and Mn in kidneys and liver from human cadavers – A case study in South Western Nigeria

In this study, autopsy tissue samples from human liver and kidneys were analysed for Cd, Cu, Pb, Zn, Hg and Mn in 25 subjects (16 males and 9 females) ranging in age from 2 to 70 years. Tissue samples that were pathologically normal were obtained at postmortem and concentrations of metals were determined. In both kidneys and liver, the concentrations of metals followed the order Cd > Hg > Pb > Zn > Mn > Cu irrespective of gender and age group, except in female kidneys where the order was Cd > Pb > Hg > Zn > Mn > Cu. Generally, males had higher concentrations of metals in both the kidneys and liver. Significant correlations of the metals were found in kidney and liver tissues.     

Use of biomarkers in zooplankton for assessment of the ‘health status’ of marine and brackish environments: a short overview

The biomarker approach has been used for 25 years to study the environmental quality of marine, brackish and freshwater ecosystems. Biomarkers may indicate health status and can be applied to organisms of all zoological phyla by destructive or non destructive methods. For 5 years we have been using this approach in zooplankton to detect ecotoxicological alterations at low levels of the food chain due to contaminants. Here we review our approach to validate and apply biomarker techniques in zooplankton. We discuss advantages, limitations, some results and future research. We indicate that biomarkers in zooplankton can be used as new indices of trophic status and ecological integrity of Italian marine coastal and lagoon environments, to be included among the tools specified by Italian law D.Lgs. 152/2006.     

Tessaria absinthioides: a possible bio‐monitor for Cd,Pb, and Cu,in the middle and lower basin of the loa river,North Chile

Some ecotoxic metals such as Cd, Pb, and Cu in Tessaria absinthioides were quantified to study its possible use as a bio‐indicator and/or bio‐monitor of these metals. This plant was chosen for its abundance in the area under study, along Chile and even in southern Latin America. For Cd, Pb, and Cu in all three parts of the plant (leaves, stems and roots) a different concentration pattern in each sampling areas was observed. In sampling areas Coya Sur and La Cascada copper and cadmium concentration decrease in order: leaves > roots > stems. In samples collected in Xalquincha the lowest concentrations of Cd and Pb were observed in stems. A maximum of cadmium concentration (9ug/gd.w. in leaves) was found in samples from La Cascada, a inflow to river Loa in Calama. High concentrations of lead were found in roots and leaves. Collected data demonstrate that the main pathway for cadmium is from ground water via roots into the plant. Some data obtained for lead and copper indicate that the influence of dust particles adsorbed on leaves and stems can be higher than uptake from ground water.     

Major and trace elements in paddy soil contaminated by Pb–Zn mining: a case study of Kočani Field,Macedonia

The objective of this study was to assess the bulk chemical composition as well as the extent and severity of heavy metal contamination in the paddy soil of Kočani Field (eastern Macedonia). The results revealed that the paddy soil of the western part of Kočani Field is severely contaminated with Pb, Zn, As and Cd in the vicinity of the Zletovska River due to irrigation with riverine water that is severely affected by acid mine and tailing effluents from the Pb–Zn mine in Zletovo. The detected total concentrations of these metals are far above the threshold values considered to be phytotoxically excessive for surface soil. The paddy soil in the vicinity of the Zletovska River was also found to exhibit elevated levels of Ba, Th, U, V, W, Mo, Cu, Sb, Bi, Ag, Au, Hg and Tl, with concentrations above their generally accepted median concentration values obtained during this study. A correlation matrix revealed that the Mn and Fe oxides/hydroxides are the most important carrier phase for several trace elements, with the exception of rare earth elements (REEs). These also represent a major sink for the observed heavy metal pollution of the soil. REEs are mostly associated with two phases: light (L)REEs are bound to K-Al, while heavy (H)REEs are bound to Mg-bearing minerals. Although there is no direct evidence of a health risk, the paddy soil in the vicinity of Zletovska River needs further investigation and an assessment should be made of its suitability for agricultural use, particularly in view of the highly elevated concentrations of Pb, Zn, As and Cd.     

Photochemistry of halogenated benzene derivatives. part xii.∗ effects of sodium nitrite on the environmental phototransformation of bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) herbicide in water: The photoincorporation of nitrite ions into bromoxynil

Photoreactions of the herbicide bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) (1) were extensively studied in water containing various concentrations of sodium nitrite with radiation of wavelengths around 313 nm. In the absence of NaNO₂, the quantum yields for the photodecomposition of the herbicide I amounted to 0.054±0.005, while such data was in the range of 0.047 ±0.005 to 0.023 ±0.003 in the presence of 0.5 to 25.0 × 10^‐3 m of the inorganic salt. These quantum yield data for the phototransformation of 1 without and with the presence of sodium nitrite followed the Stern‐Volmer equation. The rates of the photolytic destruction of bromoxynil (1) in water were slower in the presence than in the absence of NaNO₂. For example, the irradiation of the 7.8 x 10^‐6M aqueous solution of 1 in the presence of 10 mM sodium nitrite gave rise to the production of three main photoproducts, viz., 3‐bromo‐4‐hydroxy‐5‐nitrobenzonitrile (2), 4‐hydroxy‐3‐nitrobenzonitrile (3), and an “unidentified photoproduct”; 4. In the case of this photoreaction of compound 1, the percentages of maximum concentration of the photoproducts 2, 3, and 4 were achieved after 14, 44.5, and 60‐min photolyses of 1, respectively; the starting material 1 completely disappeared after 60‐min photolysis. The photoproducts 2 and 3 were identified through the interpretation of the GC‐MS data. Both thhe mass and FT‐IR spectra of the product 4 indicated the possible presence of a COOH group in 4.     

Uranium and other trace elements’ distribution in Korean granite: implications for the influence of iron oxides on uranium migration

To understand trace radionuclide (uranium) migration occurring in rocks, a granitic batholith located at the Korea Atomic Energy Research Institute (KAERI) site was selected and investigated. The rock samples obtained from this site were examined using mineralogical methods, including scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). The changes in the distribution pattern of uranium (U) and small amounts of trace elements, and the mineralogical textures affected by weathering, were examined. Based on the element distribution analyses, it was found that Fe²⁺ released from fresh biotite is oxidized in short geological time, forming amorphous iron oxides, such as ferrihydrite, around silicate minerals. In that case, the amorphous ferrihydrite does not show distinct adsorption for U. However, as it gradually crystallizes to goethite or hematite, the most U-rich phases were found to be associated with the secondary iron oxides having granular forms. This evidence suggests that the geological subsurface environment is favorable for the crystallized iron oxides to keep their structures more stable for a long time as compared with the amorphous phases. There is a possibility that the long residence of U which is in contact with the stable crystalline phases of iron may finally lead to the partial sequestration of U in their structure. Consequently, it seems that Fe-oxide crystallization can be a dominating mechanism for U uptake and controls long-term U transport in granites with low U contents.