Humic substances. Part III. sorptive interactions with environmental chemicals†

The formation of covalent binding to DNA of a carcinogen is now widely accepted to represent a classical mechanism of tumour induction in mammals. This mechanism does not operate with metals since no covalent binding of these agents to DNA does occur. Nevertheless, somatic mutations as typical consequences of DNA‐damage have been reported to be induced by metals in various model systems. Beside DNA‐alkylation such damages can be caused by changes in the conformation of DNA or in the fidelity of DNA‐repair. The activity of the repair enzymes DNA‐polymerases is indeed impaired by many metal ions at least in vitro. It is not yet established whether these mechanisms are also important in the intact mammalian organism. Much evidence has accumulated during the last years that a disturbance of the balance of cations and especially metal ions represents another possible mechanism of tumour induction. The tumours found with high doses of chelating agents such as nitrilo‐triacetic acid (NTA) have to be discussed in this context. Since most—if not—all of the speculative mechanisms of metal carcinogenesis resemble classical pharmacological reactions the existence of a threshold level is likely. So metal carcinogenesis will not be a problem of the environmental contamination at trace levels but a problem of occupational medicine.     

Toxic substances: Measures and measurements†

The formulation of a sound policy for environmental protection and toxic substances control requires knowledge of the presence and concentration of environmental contaminants. For this reason monitoring programs have been set up in the Netherlands for water, drinking water, and air pollution. The Netherlands system for air pollution, monitoring of the substances SO2, NOχ, CO, O₃ is now fully automated. Some examples will be given to show the acquisition and management and interpretation of air pollution measurements.

Various smaller projects, supported by the Department of Health and Environmental Protection include measurement of indoor air‐contaminants, contaminants in soil and hazardous waste sites, and contaminants in biotic samples such as for instance PCB's in eels and seals and mussels. Moreover a Coordinating Committee regularly collects measurements from various sources in the Netherlands regarding pesticide residues and contaminants in food.

For cost‐effective monitoring the accuracy of the measurements must be chosen with regard to the biological effect concentration of the pollutant. The necessity of proper control measurements to establish background levels and the necessity of ring‐tests to increase interlaboratory reproducibility is discussed. In cost‐effective monitoring the minimum number of measurements, which are necessary to check the effect of environmental protection measures, must be defined through proper sampling.     

Analysis,accumulation and central effects of trihalomethanes. I. bromoform†

The paper presents the results obtained in a study on the effects of organic micropollutants on the central nervous system of the rat, used herein as a suitable model for neurotoxicologic work. Bromoform, a member of the trihalomethane (THM) family, was the pollutant selected since it becomes a characteristic marker in the Barcelona potable water supply.

Analytical data on the GC‐ECD separation of THMs from other volatile halocarbons is presented. A mixed packed column 10% SE‐30/PEG 20M (94:6) at 70°C provides an adequate separation. The distribution of bromoform in rat plasma and tissues showed an accumulation in brain, kidney and fat, increasing in this order and a rapid elimination after 30 min. The effect on the central aminergic metabolism is studied by HPLC. The increased metabolic activity detected could be attributed either to an increased nervous activity, stimulating the metabolism of serotonin, or to its greater degradation.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part V†: Hypotheses and summary

The hypotheses on the de novo syntheses of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo‐p‐dioxins (PCDDs), based on known literature, are presented. Polychlorinated benzenes and polychlorinated phenols are probably key intermediates.

In the present article, hypotheses that may account for the presence of polychlorinated dibenzofurans (PCDFs) and dibenzo‐p‐dioxins (PCDDs) in the effluents from municipal and industrial incinerators are put forward. These hypotheses are based on the previously surveyed literature (Ref. 203–206) and experimental results on laboratory scale and thermodynamic calculations are considered. The interconnections of various reaction steps are speculative and no technological information was added to account for conditions in real incinerators. Conclusion of the discussions on the related subject matter, presented in the Parts I‐IV (Ref. 203–206), are also described in this paper.     

Isolation,identification, and the degradation characteristics of a thiobencarb-degrading bacterium Bacillus sp. T2北大核心CSCD

Thiobencarb, a thiocarbamate herbicide, is widely used to control weeds in rice paddies. Screening for highly efficient thiobencarb-degrading bacteria is important for the bioremediation of thiobencarb-contaminated environments. The aim of this study was to isolate and identify highly efficient thiobencarb-degrading bacteria and to identify the degradation pathway and the degrading properties. The thiobencarb-degrading strain was isolated using methods of microbiological acclimation and enrichment and was then identified using a 16S rRNA phylogenetic analysis. The degrading properties of the isolated bacterium were determined by single-factor experiments, and the degradation products were identified using gas chromatography-mass spectrometry (GC-MS). A thiobencarb-degrading strain T2, which can utilize thiobencarb as the sole source of carbon for energy and growth, was isolated from paddy soil. Strain T2 degraded more than 98.3% of 0.4 mmol/L of thiobencarb within 36 h. It was preliminarily identified as Bacillus sp. T2 according to the 16S rRNA gene analysis and from its morphological, physiological, and biochemical characteristics. The metabolic products of the thiobencarb degradation for strain T2 were identified as 4-chlorobenzyl mercaptan, 4-chlorobenzaldehyde, and 4-chlorobenzoic acid by the GC-MS. Based on metabolite identification, it was speculated that thiobencarb degradation in strain T2 was initiated by the hydrolysis of the thioester bond to produce 4-chlorobenzyl mercaptan, which was further oxidized to 4-chlorobenzaldehyde and 4-chlorobenzoic acid. The thiobencarb degradation that was initiated by the hydrolysis of the thioester bond by strain T2 is a new metabolic pathway, which provides valuable research material and reliable experimental data for revealing the metabolic process and mechanism of thiobencarb microbial degradation in soil. The strain Bacillus sp. T2 has a very high degradation efficiency, suggesting it is a good prospect for microbial remediation in thiobencarb-polluted environments. © 2018 Science Press. All rights reserved.     

Mutagenic activity of transition‐metal complexes: Relation structure‐mutagenic and antibacterial activity for some Pd(II), Pt(II) and Rh(I) complexes†

The inhibitory and mutagenic action of some Pd(II), Pt(II) and Rh(I) complexes towards various bacterial strains has been evaluated, and some correlations have been found between the chemical behaviour of the complexes and their selective biological activity: most of the complexes cause only a DNA damage repaired by the excision repair system. Particularly, the Rh(I) complexes used in this work show selective antibacterial effects on defective but no effect on wild‐type strains.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part IV†: Incorporation of inorganic chlorine into organic matter and thermochemical aromatizations

The pyrolysis and chlorination of petroleum coke in a NaCl‐KCl melt results in the production of CCl₄ and C₆Cl₆. Polychlorinated dibenzo‐p‐dioxins (PCDDs) are produced from the air oxidation and chlorination of coal using HCl or Cl₂. Smoking of tobacco containing ³⁶Cl^e provides CH₃ ³⁶Cl.

At 350°C, the rateof aromatization of 1,3‐cyclohexadiene is negligible as compared to that of 1,4‐cyclohexadiene. The aromatization of the latter diene proceeds through the molecular elimination of hydrogen; while that of 1,3‐cyclohexadiene expecially at higher pressure (10–90 Torr) and at 362–421 °C involves free radical chain mechanism.     

Cobalt speciation assay for human serum,Part II. Method validation in a study of human volunteers ingesting cobalt(II) chloride dietary supplement for 90 days

A new analytical method for determining cobalt (Co) species in human serum by size exclusion chromatography with inductively coupled plasma mass spectrometry (SEC-ICP-MS) was applied to serum samples collected from 12 human volunteers who participated in a Co(II) chloride supplement study involving ingestion of 1 mg Co/day for up to 90 consecutive days. The study protocol included determination of serum total Co by acid digestion followed by ICP-MS. Co speciation assay measurements were conducted for up to 13 time points per individual spanning from one to two weeks before dosing began to two weeks after dosing ceased. The Co speciation assay showed good recovery >91% relative to total Co measurements. Undiluted serum demonstrated uniform fractions of large molecular Co defined as Co bound to albumin and other proteins >50 kDa at 96% and the residual as small molecular Co defined as free Co(II) and <1 kDa Co-complexes for individual serum Co concentrations up to 146 μg/L. There were no dose-related changes in Co distribution. Analysis of the same serum samples with tenfold dilution in 0.1 M acetic acid led to a lower fraction of large molecular Co at 87%, with the difference between diluted and undiluted measurements being 8.4%. The difference noted between undiluted and diluted large molecular Co may be attributed to Co release from albumin. Data demonstrated that large molecular Co was the predominant Co species in both undiluted and diluted human serum over a broad range of in vivo Co concentrations, reflecting high albumin–Co binding capacity. These data validate the Co speciation assay and may be employed in understanding further the toxicokinetics and dose-response relationships for Co species.     

Reef coral reproduction in the eastern Pacific: Costa Rica, Panamá and Galápagos Islands (Ecuador). IV. Agariciidae, recruitment and recovery of Pavona varians and Pavona sp.a

The reproductive ecology of two eastern Pacific zooxanthellate coral species was examined as part of a continuing series of studies relating bleaching/mortality events caused by the El Niño–Southern Oscillation disturbance, and is described for study sites in Costa Rica, Panamá, and the Galápagos Islands (Ecuador). This study deals with the sibling agariciid species Pavona varians and Pavona sp.a over a 13?yr period (1985 to 1997). Both Pavona species are broadcast-spawners with some gonochoric, but mostly sequential hermaphroditic colonies. Minimum colony sizes (and ages) at first reproduction were 5?cm (5?yr) and 3?cm (2 to 3?yr), respectively, in P. varians and Pavona sp.a. In the Panamá and Galápagos populations, gonochoric colonies spawn eggs or sperm at least monthly. Six fecundity attributes were not significantly different in the two species, but the eggs of P. varians are white to beige and positively buoyant, and those of Pavona sp.a are dark green and neutrally to negatively buoyant. Eggs of both species lack zooxanthellae. Both species are reproductively active year-round, with maximum activity in the dry season in the nonupwelling Gulf of Chiriquí, and in the wet season in the upwelling Gulf of Panamá. Spawning is predominantly during full moon, and possibly also at new moon at most study sites. Spawning in P. varians and Pavona sp.a is 12?h out of phase, with the former species spawning ～1?h before sunrise and the latter about 1?h after sunset. The fecundity of Pavona spp. at Caño and the Galápagos Islands was much greater (19?900 to 27?900 eggs cm^?2?yr^?1) than at all Panamá sites (14?800 to 19?800 eggs cm^?2?yr^?1). Intraspecific crosses in both species resulted in swimming planula larvae after 25 to 36?h. Recruitment of P. varians was highest in Panamá, moderate in Costa Rica, and nil in the Galápagos Islands, matching, respectively, the contributions of P. varians to the pre-1982/1983 El Niño coral-population abundances in these areas. Recruitment success of P. varians at Uva Island was significantly related to maximum monthly positive sea surface-temperature (SST) anomalies that occurred in the year preceding recruitment over the period 1982 to 1996; recruitment failed when SST anomalies exceeded 1.6 to 1.9?C° during the severe ENSO events of 1982/1983 and 1997/1998.     

Maturation,fecundity, and spawning strategy of the thornback ray, <Emphasis Type=Italic>Raja clavata</Emphasis>: do reproductive characteristics vary regionally?

In Portuguese waters, thornback ray Raja clavata spawns mainly between May and January, although females and males in spawning condition are found throughout the year. The maturation process can be divided into three main phases by using information on gonad weight, oviducal gland and uterus width in females and on gonad weight, clasper length and sperm duct width in males. Females attain length-at-first-maturity at 784 mm and males at 676 mm, at ages of 7.5 and 5.8 years, respectively. In females larger than length-at-first-maturity, a resting stage was identified characterized by low gonadosomatic index and well-developed oviducal glands and uteri. These results along with the low proportion of adult females that are effectively reproducing per month demonstrated that the thornback ray cannot be considered a continuous spawner as described in other studies. Fecundity was determinate with about 35 eggs released per batch. During the spawning season, a total of four batch episodes occur indicating that the total fecundity was approximately 136 eggs per female. Regional differences may exist in the reproductive strategy of the species, namely on the duration of the spawning season, length-at-first-maturity, and fecundity, which can be related to a more intense fishing pressure in northern European waters.     

Reef coral reproduction in the equatorial eastern Pacific: Costa Rica, Panamá, and the Galápagos Islands (Ecuador). VII. Siderastreidae, Psammocora stellata and Psammocora profundacella

Two zooxanthellate, scleractinian species present in the equatorial eastern Pacific, Psammocora stellata and Psammocora profundacella, were examined in terms of their reproductive biology and ecology at four study sites, non-upwelling (Ca?o Island, Costa Rica, and Uva Island, Panamá), upwelling (Gulf of Panamá, Panamá), and seasonally varying thermal environments (Galápagos Islands). Both species were gonochoric broadcast spawners lacking zooxanthellae in mature ova. Mature gametes and spawned gonads are present around full moon; however, no spawning was observed naturally or in outdoor aquaria. Mature gametes occurred in P. stellata at Ca?o Island for nearly 6?months, and year round at Uva Island, both non-upwelling sites. Reproductively active colonies occurred mostly in the warmer months in the Gulf of Panamá and Galápagos Islands. In the Galápagos Islands, where collecting effort was greatest for P. profundacella, mature gametes were also most prevalent during the warm season. Annual fecundity was high in both species, 1.3–1.8?×?10⁴?ova?cm^?2?year^?1 in P. stellata and 1.2–2.0?×?10⁴?ova?cm^?2?year^?1 in P. profundacella. Compared to other eastern Pacific corals, P. stellata was relatively resistant to ENSO-related bleaching and mortality, especially populations inhabiting deep (12–20?m) coral communities. Rapid recovery and persistence of Psammocora spp. can be attributed to several factors: (a) relative resistance to bleaching, (b) deep refuge populations, (c) broadcast spawning, (d) protracted seasonal reproduction, (e) high fecundity, and (f) asexual propagation.     

Reef coral reproduction in the eastern Pacific: Costa Rica,Panamá, and Galápagos Islands (Ecuador). III. Agariciidae (Pavona gigantea and Gardineroseris planulata)

The reproductive ecology of Pavona gigantea Verrill and Gardineroseris planulata (Dana) was investigated in the equatorial eastern Pacific region from 1985 to 1994. These zooxanthellate scleractinian corals were adversely affected in this region during the 1982–1983 El Niño warming event. Both species were hermaphroditic, with individual colonies showing sequential cosexual development, thus resulting in dominantly outbreeding reproduction. Sexuality was mixed, with high percentages of gonochoric and hermaphroditic colonies in both species. Approximately 1:1 male-to-female gonad ratios were found in gonochoric and hermaphroditic colonies combined. Broadcast spawning was observed in P. gigantea in the Galápagos Islands, and the sudden disappearance of mature gametes and the presence of spent gonads suggest that G. planulata is also a broadcast spawner. Colonies of both species with 200 cm² (10 cm diam) live tissue were nonreproductive. Estimated ages of the youngest reproductive colonies were 11 yr for P. gigantea and 20 yr for G. planulata. The percentage of all colonies of P. gigantea with gonads at nonupwelling sites (Caño Istand, Costa Rica and Uva Island, Panamá) ranged from 37 to 47%, respectively; colonies with gonads from upwelling environments (Saboga and Taboga Islands, Panamá) ranged from 31 to 39%, respectively, and reproductively active colonies from the thermally variable Galápagos islands comprised 40% of the collections. Compared with P. gigantea, the numbers of sexually active G. planulata colonies were roughly onehalf at nonupwelling Caño Island (20%) and Uva Island (25%) sites, or less (10%) at the upwelling Saboga Island site. Peak reproductive activity in P. gigantea occurred during the rainy season at all study sites. In the nonupwelling Costa Rican (Caño Island) and Panamainan (Uva Island) sites, mean monthly sea-surface temperatures (SSTs) were high (28 to 29°C), but slightly lower than in the dry season (29°C). In the upwelling Gulf of Panamá (Saboga and Taboga Islands), reproduction occurred after mean monthly SSTs increased from 24 to 28–29°C. In the Galápagos Islands, reproductive activity peaked during sea warming, when mean monthly SSTs reached 25°C. Sexually active colonies of G. planulata, present only at the main collection sites of Caño and Uva Islands, were also observed during the wet season. The presence of mature or spawned gonalds in both species mostly around new and full lunar phases suggests that spawning is at least weakly synchronized with moon phase. Fecundity estimates disclosed the following nonsignificant differences between sites for P. gigantea, expressed as egg production cm^-2 colony surface surface yr^-1: Galápagos (10 300 to 30 800), Uva Island (4900 to 9800), Caño Island (1800 to 7400), Saboga Island (600 to 1300) Taboga Island (1200 to 2400). Fecundity estimates for G. planulata were considerably lower: Uva Island (700 to 1400), Caño Island (500 to 1000). The sexual recruitment of P. gigantea into El Niño-Southern Oscillation (ENSO) 1982–1983-disturbed, equatorial eastern Pacific coral communities has been low, with only moderate recovery evident since 1983. G. planulata has revealed no sexual recruitment where seed populations are absent or rare (Caño Island, Galápagos Islands), and only low recruitment (Panamá) in areas with colonies that survived the ENSO disturbance.     

Migration of aluminum from food contact materials to food—a health risk for consumers? Part II of III: migration of aluminum from drinking bottles and moka pots made of aluminum to beverages

Background

Drinking bottles and stove-top moka pots made of aluminum have become very popular. Storing drinks in bottles and preparing coffee in a moka pot may result in the migration of aluminum to the beverage.

Results/Conclusions

In a systematic study of aluminum drinking bottles, it has been shown that drinking a mixture of apple juice and mineral water in an aluminum bottle may reach 86.6% of the total weekly intake (TWI) for adults, and drinking tea from an aluminum bottle may exceed the TWI (145%) for a child weighing 15 kg. In contrast, preparing coffee in an aluminum moka pot results in a maximum of 4% to TWI, if an average of 3.17 L coffee is consumed per week, even if the pots are washed in the dishwasher, against the explicit instructions of the manufacturer.