Cross‐sectional epidemiological study on the lead burden of children and workers in Greece

Exposure of the general population to lead in the environment is mainly caused by motor traffic exhaust and by industrial pollution. The aim of the study in Greece was to assess lead exposure in children living in point source impacted areas (Lavrion and Aspropyrgos‐Eleusis) using the biological monitoring parameter “blood lead concentration”;.

In addition, workers of a lead smelter, a battery plant and an oil refinery were investigated in these areas at the same time.

Five hundred and thirty‐four children and 105 workers took part in this investigation.

The highest blood lead levels (mean: 24.16 μg/100ml; range: 10.40–60.49 μg/100 ml) were found in children living in a 500m‐area around the lead smelter at Lavrion. Blood lead decreases corresponded to the increasing distance from the emitter. Nevertheless the values of children living in a 1500 m distance to the smelter are significantly higher than those of children living next to other kinds of industrial lead sources.

The mean values of the children living in the two industrial towns were manifold higher than those of the control group.

The blood lead levels of the investigated workers did not exceed the German BAT‐value (Biologischer Arbeitsstoff‐Toleranzwert) of 70 μg/100ml.     

Effect of fluoride content in drinking water in Tricity on its concentration in urine of pre‐school children

Fluorides were analysed in drinking water and in urine of pre‐school children from different districts of Tricity (Gdańsk, Gdynia and Sopot). Concentration of fluorides in urine was found to depend on their content in drinking water. The two years (1997–98) study was made for 15 preschool children populations; each numbering in 10–20 individuals. The fluorides were determined by flouroselective electrode potentiometry.     

Total arsenic concentrations in Chinese children’s urine by different geographic locations,ages, and genders

Little is known about the variation of Chinese children’s exposure to arsenic by geography, age, gender, and other potential factors. The main objective of this study was to investigate the total arsenic concentration in Chinese children’s urine by geographic locations, ages, and genders. In total, 259 24-h urine samples were collected from 210 2- to 12-year-old children in China and analyzed for total arsenic and creatinine concentrations. The results showed that the upper limit (upper limit of the 90% confidence interval for the 97.5 fractile) was 27.51 µg/L or 55.88 µg/g creatinine for Chinese children. The total urinary arsenic levels were significantly different for children in Guangdong, Hubei, and Gansu provinces (P < 0.05), where the upper limits were 24.29, 58.70, and 44.29 µg/g creatinine, respectively. In addition, the total urinary arsenic levels were higher for 2- to 7-year-old children than for 7- to 12-year-old children (P < 0.05; the upper limits were 59.06 and 44.29 µg/g creatinine, respectively) and higher for rural children than for urban children (P < 0.05; the upper limits were 59.06 and 50.44 µg/g creatinine, respectively). The total urinary arsenic levels for boys were not significantly different from those for girls (P > 0.05), although the level for boys (the upper limit was 59.30 µg/g) was slightly higher than that for girls (the upper limit was 58.64 µg/g creatinine). Because the total urinary arsenic concentrations are significantly different for general populations of children in different locations and age groups, the reference level of total urinary arsenic might be dependent on the geographic site and the child’s age.     

Aqueous high‐temperature chemistry of arsenic‐containing compounds in water at 300°C

Arsenic compounds, and especially organo‐arsenic derivatives, are highly toxic and many have been manufactured as chemical warfare agents. This study was designed to provide background information relevant to the potential application of aquathermolysis techniques for the detoxification of such potent military warfare agents. Six arsenic‐containing compounds with structural features which mimic known agents were studied in neutral superheated water: 4‐aminophenylarsine oxide, 4‐arsanilic acid, 4‐nitrophenylarsonic acid, 5, 10‐dihydro‐10‐ethylphenarsazine, tetraphenylarsonium chloride hydrate, and (3‐cyanopropyl)dimethyl(2‐phenethyl)arsonium bromide. Most of these compounds were moderately susceptible to hydrolysis for 1h at 300°C. o‐ and p‐Aminosubsituted arsenic compounds were more reactive than compounds with an electron‐withdrawing group substituent. Aromatic C—As bonds were more resistant to cleavage than aliphatic C—As bonds.     

Study on polychlorinated dibenzo‐p‐dioxins and dibenzofurans in rivers and estuaries in Osaka Bay in Japan

In order to search the source of polychlorinated dibenzo‐p‐dioxins (PCDDs) and dibenzofurans (PCDFs) in blue mussel in Osaka bay, sediments from Osaka bay and from rivers running near an urban municipal incinerator were analysed for PCDDs, PCDFs and PCBs. The river and estuary sediments were all found to be contaminated with PCDDs at average levels of 9.8 and 12ppb on the dry basis, PCDFs of 7.8 and 5.1 ppb, and PCBs of 1600 and 1300ppb, respectively. The two sediments contained similar profiles of specific isomers and congeners of PCDDs and PCDFs with each other. In addition, there was observed positive close correlations between PCDD and PCDF levels in the two specimens as well as fly ash from urban municipal incinerators. These allow the conclusion that the main source of the two chemicals in Osaka bay is fly ash from waste incineration.     

Soil arsenic surveys of New Orleans: localized hazards in children’s play areas

Arsenic (As) ranks first on the 2005 and 2007 hazardous substances priority lists compiled for the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). This study describes two New Orleans soil As surveys: (1) a survey of composite soil samples from 286 census tracts and (2) a field survey of soil As at 38 play areas associated with the presence of chromated-copper-arsenate (CCA)-treated wood on residential and public properties. The survey of metropolitan New Orleans soils revealed a median As content of 1.5 mg/kg (range <0.2–16.4) and no distinctive differences between the soils of the city core and outlying areas. Play area accessible soils associated with CCA-treated wood (N = 32) had a median As of 57 mg/kg and 78% of the samples were ≥12 mg/kg, the Louisiana soil As standard. The field survey of play areas for CCA-treated wood (N = 132 samples at 38 sites) was conducted with a portable energy-dispersive X-ray fluorescence (XRF) analyzer. Seventy-five of 132 wood samples (56.8%) were deemed CCA-treated wood. Of the 38 play areas surveyed, 14 (36.8%) had CCA-treated wood. A significant association (Fisher’s exact p-value = 0.348 × 10⁻⁶) was found between CCA-treated wood and soil As (N = 75). At one elementary school CCA-treated woodchips (As range 813–1,654 mg As/kg) covered the playgrounds. The situation in New Orleans probably exists in play areas across the nation. These findings support a precautionary program for testing soils and wood for hazardous substances at all play areas intended for children.     

Effects of the Ellagic acid on the N‐Acetyltransferase activity and Acetylation of 2‐aminofluorene in the rat

The effects of the ellagic acid on the in vitro and in vivo acetylation of 2‐aminofluorene were investigated in male Sprague‐Dawley rats. For in vitro examination, cytosols with or without ellagic acid co‐treatment showed different percentage of 2‐aminofluorene acetylation. For in vivo examination, pre‐treatment of male rats with ellagic acid (10 mg/kg) 24h prior to the administration of 2‐aminofluorene (50 mg/kg) resulted in a 26% and 29%, respectively, decrease in the urinary and fecal recovery of N‐acetyl‐2‐aminofluorene, and a 37% decrease in the metabolic clearance of 2‐aminofluorene to N‐acetyl‐2‐aminofluorene. This is the first demonstration that ellagic acid decrease the N‐acetylation of carcinogens in vitro and in vivo.     

Determination of pentachlorophenol in human urine using solid phase extraction and GC‐MS analysis with stable isotope dilution

A method for the determination of pentachlorophenol (PCP) in human urine was developed. Urine samples were fortified with ¹³C₆‐IabeIed PCP and hydrolyzed with sulfuric acid prior to extraction. The urine samples were then passed through preconditioned solid phase extraction cartridges containing octadecylsilane adsorbent. The PCP was subsequently eluted from the cartridge with ethyl acetate and converted to pentachloroanisole prior to GC‐MS analysis. GC‐MS quantitation was performed using the technique of stable isotope dilution. Percent recoveries averaging 100, 97, and 111% were obtained for replicate urine samples fortified with approximately 2, 20, and 200 ng/mL of PCP, respectively. The method detection limit was estimated to be 0.2 ng/mL.     

Feathers of white stork Ciconia ciconia chicks in North‐Eastern Greece,as indicators of geographical variation in mercury contamination

Variations in mercury contamination of ecosystems were assessed among areas of northeast Greece by sampling and analysing feathers of White Stork chicks. Mercury concentrations in stork chick feathers were highest in an area known to be affected by riverborne mercury pollution, and were lowest in an inland area away from rivers or lakes. Although regurgitated pellets indicated a predominantly terrestrial diet among White Stork adults, variation in mercury concentrations among localities seemed to relate to pollution of aquatic rather than terrestrial foods of storks. Toxic thresholds of mercury in this species are unknown, but the highest concentrations, observed in chicks from the Axios Delta (up to 4.1 μg.g^‐1 in feathers) were well above levels having toxic effects in gamebirds. Mercury concentrations in chick feathers increased slightly with chick age and with brood size, but these trends were small by comparison with variations among localities.     

Concentrations of polychlorinated dibenzo‐p‐dioxins and dibenzofurans in outdoor air of North‐Rhine‐Westphalia,Germany

Measurements of polychlorinated dibenzo‐p‐dioxins (PCDD) and dibenzofurans (PCDF) in outdoor air of North‐Rhine‐Westphalia were carried out. Fifty‐six samples were taken at different sites in areas of different land use and emission structures. A special filter system allowed analysis of the gas and particle phases separately. It was found that higher chlorinated PCDD/PCDF (7 or 8 chlorine atoms) are collected on glass fiber filter and lower chlorinated PCDD/PCDF (tetra‐ and penta‐CDD/CDF) are absorbed on polyurethane foam. The following isomers were determined: OCDD, OCDF and 11 isomers with chlorine substitution in 2,3,7,8‐position as well as the sum of TCDD, PeCDD, HxCDD, HpCDD, TCDF, PeCDF, HxCDF, HpCDF and the sum of PCDD (4–8) and PCDF (4–8). No 2,3,7,8‐TCDD could be detected but 2,3,7,8‐TCDF was found at 15 sites. Mean concentration in the Rhine‐Ruhr‐District for the sum of PCDD (4–8) and PCDF (4–8) was 3.2pg/m³ and 5.5pg/m³ respectively. Detection limit for TCDD and PCDD/PCDF (5–8) was 0.1–0.2 pg/m³ and 0.005–0.015 pg/m³ respectively. There is no significant indication that 2,3,7,8‐chlorinated isomers of PCDD/PCDF are predominantly decomposed by photochemical reactions in outdoor air.     

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.     

Effects of lead and selected pyrethroids/piperonyl butoxide alone and in combination on Na,K‐ATPase

In vitro effects of Pb²⁺, the pyrethroid insecticides cypermethrin, fenvalerate and the syner‐gist piperonyl butoxide on sodium‐potassium‐activated adenosine triphosphatase (Na,K‐ATPase) from dog kidney were determined. Pb²⁺ with an estimated IC50 value of 5.2 μM was found to be a potent inhibitor of Na,K‐ATPase activity, whereas Na,K‐ATPase was less sensitive to the pyrethroids tested and piperonyl butoxide. Investigation with circular dichroism (CD) spec‐troscopy showed that inhibition occurs through conformational changes of the α‐subunit of the enzyme. The kinetic characteristics of inhibition of Na,K‐ATPase with varying substrate (ATP) concentrations as well as with varying Na⁺ concentrations exhibited a competitive type of inhibition with Pb²⁺ in the μM range. With Pb²⁺ alone in the enzyme assay no conformational changes of the protein could be observed which confirmed the assumption that Pb²⁺ can bind to the Na⁺ binding site of the α‐subunit. Uncompetitive type of inhibition occurred with varied K⁺ concentrations demonstrating that this cation binding site is not affected directly by Pb²⁺.

Complete reversal of Pb²⁺ by DTT confirms that a possible target for interaction of this heavy metal ion with Na, K‐ATPase are specific SH groups.

Synergistic effects could only be determined with higher Pb²⁺ concentrations of 3, 5 and 7 μM plus piperonyl butoxide while all other combinations with this heavy metal plus organic substances where of the additive type. With CD spectroscopy also only additive effects were observed. These results demonstrate that higher concentrations of piperonyl butoxide favor the binding of Pb²⁺ to the Na⁺ binding site by conformational changes of the protein.     

The use of the embryo‐culture techniques in the research on the Teratogenic and Mutagenic properties of metals†

Actually, embryos can be cultured from the one‐cell stage up to the blastocyst stage, and their development can be easily monitored at any time: severe effects caused by toxic compounds are traduced by rapid embryonic death, less pronounced effects can be expressed by a lowered cleavage activity or by an arrest of the development from a particular stage. The system can be improved by transferring the embryos at the blastocyst stage in another more complete medium where they can “implant”; and form an inner cell mass with differentiated ectoderm and endoderm. Since last years, it has also become possible to culture postimplantation rodent embryos for short periods involving a number of particularly critical stages of organogenesis, such as the formation and closure of the anterior neuropore. Embryo‐culture also represents a useful system to study cytogenetic effects of chemicals which are often linked to lethal or teratogenic effects. These different possibilities are illustrated by examples of studies already performed with metals, and dealing with their teratogenic and/or cytogenetic effects on pre‐ and postimplantation rodents.     

Metal speciation in sediments of polluted and non‐polluted lakes

A five‐step extraction procedure for metal speciation studies (copper, lead, nickel, manganese and zinc) was applied to the analysis of lake sediments characterised by different environmental features. A different partition of metals into the several metal forms was observed. Both the metal fraction sorbed or co‐precipitated on hydrous Mn‐oxides (especially lead and zinc) and that bound to organic matter (especially copper) are high in some samples. A prevalently anthropogenic origin of these metals may be hypothesised on the basis of existing knowledge of the equilibrium and change phenomena occurring among water, particulate and sediments. Conversely, the non‐solubilised forms of metals are abundant in the sediments of lakes that are certainly not polluted. The concentration of manganese is very high in the sediments of Antarctic lakes; sequential extractions show its lithogenic origin. In conclusion, a knowledge of the different types of metal associations in sediments and their percentage can facilitate understanding of both natural and anthropogenic metal enrichment of aquatic systems.     

Rose Bengal‐sensitized photooxygenation of chlorohydroxyaromatic contaminants in water: A kinetic study

A kinetic study of the RB‐sensitized photooxygenation of a series of chlorohydroxyaromatic (ClArOH) water contaminants (phenolic and dihydroxybenzene derivatives) has been carried out. In addition, an exhaustive study on the possible interactions of RB electronically excited triplet and singlet states with ClArOH was also developed. The determination of relative rates of oxygen uptake upon sensitized irradiation, employing auxiliar selective quenchers of oxygen active species, indicate the contribution of both singlet molecular oxygen (ca. 71%) and Superoxide ion (ca. 26%) as the reactive pathways for ClArOH degradation. The substitution by chlorine atoms in position meta greatly decrease the photooxygenation rate of the phenolic derivatives. For the dihydroxybenzene series, increase in nuclear chlorination parallels a decrease in the photodegradation rate.

Outdoors sensitized solar irradiation experiments on different ClArOH mixtures leads to measurable levels of oxygen after a few minutes exposure. From the environmental point of view, and ruling out the possibility of direct‐irradiation photoreactions, sensitized photooxygenation appears as an alternative pathway for ClArOH degradation, in competence with other naturally‐occurring photoprocesses involving reactive transient species.     

Groundwater quality in the major industrial area of Thessaloniki,Greece part 1: Chemical composition‐geochemical processes

Adsorption rates of Sb(V) ions on an activated alumina (AA) were analyzed by batchwise experiments, while the continuous adsorption, desorption, regeneration of AA, and multiple reuse cycles were studied by flow column tests. The adsorption rates increased quickly with the increases of shaking speed and operation temperature. The adsorbed Sb(V) ions were desorbed easily by a 50 mM NaOH solution, and a 41–90 times concentrated Sb(V) solution was yielded correspondingly. AA was effectively regenerated by desorption operation and ca. 93% of the initial adsorption capacity was retained after six times adsorption/desorption cycles.     

α1-Microglobulin levels and correlation with cadmium and other metals in urine of non-smoking women among general populations in Japan

The present study was initiated to examine urinary α₁-microglobulin (α₁-MG-U) levels among non-smoking women in the general population in Japan. A previously established database on spot urine samples from adult woman volunteers in 10 non-polluted areas all over Japan was re-examined. The data examined were on α₁-MG-U, cadmium, calcium, magnesium and zinc levels in urine (Cd-U, Ca-U, Mg-U and Zn-U, respectively), urinary creatinine (CR or cr), urine specific gravity (SG or sg), smoking habits and age. Thus, 8975 never-smoking women were selected for statistical analyses. The grand geometric mean (GM) for α₁-MG-U among the population was 2.1?mg/L or 2.5?mg/g?cr, depending on the correction for urine density. It was 1.1?µg/L or 1.3?µg/g?cr for GM Cd-U. The inter-area difference in α₁-MG-U was <1.5?mg/g?cr or <0.7?mg/L; the area with the highest or lowest GM Cd-U was not always highest or lowest in GM α₁-MG-U. The correlation coefficient (0.53) between log?Cd-U and log?α₁-MG-U (both without urine density correction) became substantially smaller when the analyte levels were corrected for CR (0.25) or SG (0.26). In multiple regression analysis, the power of influence of the five independent variables (log?Cd-U, Ca-U, Mg-U, Zn-U and age) in combination was small (R ²?≦?0.13). In contrast, logistic regression analysis suggested that α₁-MG-U might be elevated as a function of an increase in Cd-U, depending on the cut-off values. Discussion was made on dose (Cd-U_cr) and response (α₁-MG-U_cr) relationship based on information available in literatures to show that the increment in α₁-MG-U_cr per Cd-U_cr was much greater when Cd-U_cr was large, e.g., in excess of 10?µg/g?cr.     

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.