Recent advances in arsenic mutagenesis and carcinogenesis†

Arsenic is ubiquitously distributed in nature and is released into the environment through non‐ferrous smelting operations, generation of power from coal, and agriculture.

Epidemiological studies have shown that the incidences of epidermoid carcinomas of the skin and lungs, and of pre‐cancerous dermal keratoses are significantly increased in human subjects exposed to arsenic compounds by oral or respiratory routes. The negative results obtained on animals treated with arsenicals suggest strongly that this metal is probably a cocarcinogen.

The results of the short‐term tests suggest that the cocarcinogenic properties of arsenic could be related to its ability to inhibit DNA repair.     

Analysis of the cyanotoxins anatoxin-a and microcystins in Lesser Flamingo feathers†

Feathers from carcasses of the Lesser Flamingo (Phoeniconaias minor), which had died after ingesting cyanobacterial toxins (cyanotoxins) contained between 0.02 and 30.0?µg microcystin-LR equivalents per gram of feather according to HPLC and ELISA analysis of feather extracts. Anatoxin-a was detected less frequently in the Lesser Flamingo feathers, up to 0.8?µg anatoxin-a per gram of feather being recorded. When feathers from different body regions were analysed and compared for microcystins and anatoxin-a, wing feathers were found to contain the highest concentrations of these cyanotoxins, the order of concentration and frequency of analytical detection being wing?>?breast?>?head. Consistent with the presence of the microcystins and anatoxin-a in gut contents and the livers of the dead birds and negligible in vitro adsorption to feathers, the cyanotoxins associated with the feathers of the dead wild flamingos are inferred to be primarily of dietary origin.     

Arsenic and chromate removal from water by iron chips—Effects of anions

The purpose of this study is to estimate the removal efficiency of As and Cr (VI) by one kind of industrial waste — iron chips, as well as to estimate the effects of typical inorganic anions (sulfate, phosphate, and nitrate), and typical organic anions (citrate, oxalate, and humate) on As or Cr (VI) removal. The results showed that 98% of As (V) and 92% of As (III) could be removed from aqueous phase by the iron chips within 60 min. Compared with As species, Cr (VI) was removed much more rapidly and efficiently with 97% of Cr (VI) being removed within 25 min. The removal efficiency for arsenic was in the order: As (III) (sulfate), As (III) (nitrate) or As (III), As (III) (humate), As (III) (oxalate), As (III) (citrate), As (III) (phosphate), and for chromate was in the order: Cr (VI) (sulfate), Cr (VI) (phosphate) or Cr (VI) (nitrate) or Cr (VI) (oxalate), Cr (VI), Cr (VI) (citrate), Cr (VI) (humate). In all the treatments, pH level increased with time except for As (III), the removal of which was either without anions or in the presence of humate or nitrate.     

Biogeochemistry of aromatic hydrocarbons in the benthos of microcosms†

Investigations into the fate of petroleum compounds in the marine environment were carried out using experimental microcosms of two sizes and designs. Aromatic hydrocarbons or No. 2 fuel oil were spiked to the water of a 13 m³ continuous flow system and to a 2281 recycled flow system. The transport and alteration of this oil was traced in the sediment and benthic organisms (Glycera americana, Crepidula sp., and Nephtys incisa) of these microcosms. Measurable contamination was found in both sample types. The aromatic hydrocarbon distribution, including relative isomeric distribution (e.g., C₂‐phenanthrenes) was found to be different in sediment and in organisms from that which was originally introduced to the experimental microcosm. Differences in isomer distribution between Glycera and Crepidula were also detected. Based on the experimental data: molecular weight and specific isomeric form, biochemical processes, solubility, and particle adsorption/desorption influence the fate of petroleum compounds in benthic ecosystems.     

Investigation of the sources of aliphatic hydrocarbons in the mussel Mytilus edulis from north sea oil production platforms by Capillary glc and CGCMS†

Aliphatic hydrocarbons isolated from mussels collected over a 20 month period from three North Sea Forties field oil production platforms have been examined by capillary gas chromatography and gas chromatography‐mass spectrometry.

The biological hydrocarbons consist predominantly (300–700 μh g^‐1 lipid) of C₃₁ and C₃₃ n‐alkenes with 2, 3 and 4 double bonds probably derived from a dietary intake of Emiliania huxleyi, a microscopic coccolithophorid alga. In some of the mussels C₁₈, C₂₀ and C₂₂ n‐alkanes are present in unusually high abundance compared to their odd carbon number homologues. Possible reasons for this distribution are discussed.

The concentrations of fossil fuel hydrocarbons (mainly unresolved complex mixtures) in the mussels ranged from 330 to 5,298 μg g^‐1 of lipid. No significant increase in values was detected two months after the start of discharge of treated Forties production water from the Forties D platform.

To determine the pollutant hydrocarbon sources, the sterane and terpane distributions of hydrocarbon fractions isolated from the mussels and from a number of fossil fuels, including Forties crude oil, were examined by mass fragmentography. The steranes in the mussels from the Forties C and D platforms contained higher proportions of regular 14α(H), 17α(H) components than Forties oil in which the steranes were mainly 13ß(H), 17α(H) diasteranes. In addition, the terpane distributions of the mussel fractions differed markedly from that of Forties crude oil, particularly in the relative abundance of diterpanes to triterpanes, which was higher in the mussel fractions than in the oil, and in the absence of 17α(H), 18α(H), 21ß(H)‐18, 30‐bisnorhopane, a known component of Forties crude. Furthermore, the ratio of C₂₉ to C₃₀ triterpanes was greater than unity in the mussels but much less than unity in the Forties oil. These data preclude Forties or other similar North Sea crudes as the major source of pollutant aliphatic hydrocarbons in the mussels. The relative concentrations and distributions of steranes and triterpanes suggest that the most likely source of pollutants is a Middle Eastern based oil derived either from rig activities, or from background pollution in the North Sea. The low concentration of ≥ C₂₇ steranes in the more polluted mussels (e.g. Forties B; UCM > 200 ppm dry wt.) suggests that gas oils used on the platforms may be the major source of petrogenic hydrocarbons in these samples.     

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.     

Source and Distribution of Heavy Metals in Food†

Diet is the major route of exposure to contaminants, therefore food monitoring programs are essential to estimate the degree of human risk. We present a study undertaken in Austria dealing with the total uptake of mercury, cadmium, arsenic and lead. The dates were calculated from diet as well as from commercial food. Higher contaminated foodstuffs are registered and a comparison was made between body burden of babies and adults on the basis of bodyweight. It was pointed out, that cooked or washed food ready to eat has a lower burden of lead and cadmium than non prepared food due to household processing, which may decontaminate food to some extent’ Arsenic content was not reduced, because it is bound chemically and not primarily deposited on the surface of food such as in the case of lead. It was mentioned that the type of compound plays an important role in the assessment of action of those elements on humans.

Their biological activity is not necessarily related to their concentration in food. As in the case of selenium and chromium one has to take into consideration that there is a narrow range between benefit and harm, toxicity, and minor supply.

Therefore we conclude, that due to interactions of elements, their different biological activity and due to the difference of compounds present in food, we have to relativate the terms toxicity and essentiality. Then we can get a more profound insight into the problems of trace elements in food.     

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.     

Alkylation of metals and the activity of metal‐alkyls†

The biochemical basis for resistance to metal ion toxicity is emerging though it is complicated by the different resistance mechanisms. Several strategies for resistance to toxic metal ions have been identified:

1. The development of energy driven efflux pumps which keep toxic element levels low in the interior of the cell. Such mechanisms have been described for Cd(II) and As(V).

2. Oxidation (e.g. AsO^2‐ to AsO₄ ^3‐) or reduction (e.g. Hg²⁺ to Hg⁰) can enzymatically and intracellularly convert a more toxic form of an element to a less toxic form.

3. The biosynthesis of intracellular polymers which serve as traps for the removal of metal ions from solution such as traps have been described for cadmium, calcium, nickel and copper.

4. The binding of metal ions to cell surfaces.

5. The precipitation of insoluble metal complexes (e.g. metal sulfides and metal oxides) at cell surfaces.

6. Biomethylation and transport through cell‐membranes by diffusion controlled processes.

In this short review I shall discuss the implications of biomethylation as a detoxification mechanism for microorganisms as well as for certain higher organisms.     

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.     

Comments on the Carcinogenicity and Mutagenicity of metals and their compounds†

The carcinogenicity of metals has received extensive study, both epidemiologically and in the laboratory. These have included case reports of occasional human occurrence or clusters of cancer cases as well as extensive epidemiologic studies; in addition, there has been significant laboratory research on the whole animals and in vitro systems. This body of information will be examined selectively.

I will not in this paper attempt a comprehensive review of the mutagenicity and carcinogenicity of metals and their compounds. Rather, I will attempt to set forth some historical perspectives, and to comment on some current gaps and needs.

Other papers in this workshop have presented thorough and very current reviews of most of the topics briefly noted in this presentation and do not require repetition here.

The cancer issue has been studied and reported on far more extensively than that relating to heritable mutations. There has been in recent years increasing interest in the use of short term tests for mutagenicity and cell transformation. These, however, are primarily with respect to their relationship to cancer production rather than to germ cell injury. Interest in cancer from metal compounds goes back a long time; in fact, one of the earliest reports was on the carcinogenicity of arsenic not many decades after the pioneering report of Sir Perceval Pott on cancer in chimney sweeps. Since then cancer has been definitely associated in humans with chromium compounds, nickel, and with less assurance but probably definitely with beryllium and cadmium. The confirmation of these findings in laboratory animals has been uneven. In the case of arsenic, for example, there has been only limited success in the production of cancer in laboratory animals with arsenic.

Many other metals have been found in laboratory studies to produce cancer, although with most of these, evidence of production of cancer in humans is either absent or extremely uncertain.

The extensive body of recent information relating to the testing of metals with a variety of short term tests will be briefly reviewed.     

The effect of cadmium upon the structure of the olfactory nerve in the young pike †

Some recent experiments have shown with autoradiographic methods the axonal transport of cadmium along the olfactory nerve of the salmon trout.² We should determine in our experiments the effect of cadmium upon the olfactory nerve at histological level using optical microscopy technics.     

The application of analytical techniques to the understanding of chemical processes occurring in the atmosphere†

The science of atmospheric chemistry has expanded enormously over the last decade. In the stratosphere it has become apparent that small traces of a number of gases can perturb the earth's ozone layer. In the troposphere it is now realised that a general oxidation process is occurring which involves several free radicals and a large number of stable gaseous molecules containing the elements H, C, N, O, S, P, F, Cl, Br and I. In areas close to centres of large population this leads to the phenomenon of photochemical smog and in more remote areas it leads to excess acidity in rainwater.

In order to gain information on these problems and understand the underlying causes, many new analytical techniques have been developed. These are based mostly on chemilu‐minescence, laser spectroscopy, gas chromatography and mass spectrometry. Some examples of the application of these techniques will be given with emphasis placed on the role of GC/MS (gas chromatography combined with mass spectrometry).     

The interethnic differences of the human serum paraoxonase polymorphism analysed by a quantitative and a qualitative method †

The polymorphism of the human serum paraoxonase¹ was analyzed by two distinguished methods in six different ethnic groups (Caucasians, Mongoloids, Negroids), using (1) the Computer Method² and (2) the Carro‐Ciampi Method³‘⁴. Analysis of the response of the enzyme activities to salts resulting in low and high activity ratios.

Comparison of the results:

In Caucasians we distinguished three phenotypes by the Computer method. The polymorphism was governed by two alleles. The Hardy‐Weinberg rule for a two‐allele model was valid. Individuals belonging to the homozygotic group with low activity had a low activity ratio (Carro‐Ciampi method). With both methods a frequency between 57% and 61% was observed for this group. Individuals with medium and high activity had a high activity ratio.

In Negroids and Mongoloids samples we found (by the Computer method) a low activity group (Ghanaians 9.6%, Jamaicans 13.6%, Indonesians 6.7%, Koreans 19.6%). The Hardy‐Weinberg rule for a two‐ or three‐allele model was not valid. Individuals belonging to the low activity group had a low activity ratio, all individuals with higher activity a high activity ratio (Carro‐Ciampi method).

Our results suggest that the members of the low activity group in the three races are homozygote for an identical allele.     

Cesium inhibition of motor activity in comparison to Lithium and Rubidium †

The biochemical and toxicological significance of cesium is scarcely understood, and could be evaluated in comparison with lithium widely used as a psychotropic drug. Two male Wistar rat groups of 200–220 g are administered independently, lithium, sodium, rubidium and cesium chloride, in doses of 3mEq/Kg/day (0.024 Eq/L drinking water) during 29 days. Motor activity was measured after the injection of 70 mg pargyline/Kg animal i.p. as inhibitor of MAO A + B with an activimeter of Tedeschy type. Accumulative movements per minute are presented in function of time. Total brain proteins, alkaline and acid phosphatases and blood parameters, haematocrit, haemoglobin and erythrocytes, were determined.

The maximal increase of motor activity was seen in rats treated with RbCl 2 h after the pargyline administration and the diminution was Rb>Li>Cs. Cesium induced a decrease of the total serum protein concentration from 6.39 ± 0.1 to 5.8±0.5mg/100ml serum in controls. Acid and alkaline phosphatase were decreased in cesium treated rats. The three determined blood parameters, haematocrit, haemoglobin and erythrocytes, show also a decrement with cesium treatment compared to the control ones.     

Polychlorinated biphenyls and organochlorine pesticides in amniotic fluids of pregnant women in south-central Turkey†

The concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were determined in amniotic fluid of 200 pregnant women from the Cukurova region of Turkey. The concentrations of OCPs [hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), dichlorodiphenyl trichloroethane (p,p′-DDT), and various metabolites], and different PCB congeners (28, 52, 101, 118, 138, 153, 180) were determined by gas chromatography with electron capture detection as follows: HCB 6.6 ± 4.7, ΣHCH 21.6 ± 14.2, ΣDDT 12.5 ± 7.5, and ΣPCBs 74.0 ± 54 ng mL^?1. Correlations of maternal or gestational age and levels of OCPs and PCBs were not significant. The levels of these organochlorine compounds (OCs) were below detection limit for 5% of the samples, 80% contained more than one OC. This study illustrates that prenatal exposure of a fetus to OCs is prevalent in the Cukurova region.     

Environmentally significant photochemistry of chlorinated benzenes and their derivatives in aquatic systems†

The pollution of soil and aquatic environments by chlorinated aromatic pollutants (CAPs) such as polychlorobenzenes (PCBzs), polychlorophenols (PCPs), polychloro‐diphenyl ethers (PCDPEs), phenoxyacetic acids, etc., creates growing public anxiety. Phototransformation is an important process for pollutants in aquatic systems. This article extensively reviews the environmentally significant solution phase photochemistry of PCBzs as well as other CAPs derived therefrom. The paper includes photochemical fate of these CAPs at wavelengths >285 nm on the one hand and their photolysis in solution in aquatic systems on the other. In this article, photolytic reductive dechlorination and isomerization of PCBzs are reviewed together with the photoformation of several products including polychlorobiphenyls (PCBs) from PCBzs. Recently developed phenomena of photoincorporation of PCBzs into humic model monomers is also described. This review also describes the environmental photochemistry of chlorobenzene derivatives, namely, α‐substituted p‐chlorotoluenes of the general structure p‐ClC₆H₄CH₂‐X (X = H, Cl, CN, COOH and OH), di‐through pentachlorophenols, PCDPEs (having Cl_1–5 contents) with and without o‐OH substituents, and 2,4‐di‐ and 2,4,5‐trichlorophenoxyacetic acid (2,4‐D and 2,4,5‐T, respectively) as well as their esters and some formulations.     

Speciation and carcinogenic classification—some limits of assessment and prevention procedures—the case of “nickel”

The speciation of nickel is of the highest importance for the definition of lists of substances for regulatory activity in terms of prevention, regarding possible cancer risk. A review is made of the different attitudes of outstanding administrations in front of nickel speciation. Some of them show a maximum of care in chemical definition, others reflect a lack of scientific rigor leading to generic classifications, more or less abusive. The great complexity of the chemistry and physicochemistry of nickel imposes the “two‐level speciation concept” (chemical and physicochemical), at least for compliance with the “Good Laboratory Practice” as far as experimental toxicology is concerned. Recommendations are exposed for the attention of toxicologists and regulators who have been for some years now extremely solicited for prevention aims.     

Alleviation of nickel stress by halophilic bacteria in mungbean (Vigna radiata)北大核心CSCD

Mungbean is an important, short-duration legume crop with high nutritive value for poor families, where protein and micronutrient scarcity are most pervasive. In developing countries, like Pakistan, where mungbean is one of the greatest sources of protein for underprivileged people, salinity and metal stresses are drastically limiting its yield. Therefore, it is necessary to explore the ways for promoting the growth of mungbean under stressed conditions. This study provides the basis for the use of two previously isolated halophilic and nickel-resistant bacteria [Bacillus subtilis and Halomonas aquamarina (1)] in promoting the growth of mungbean plant under nickel-stressed environments. These bacterial strains were previously found to improve the growth of plants under salinity because of their good biofilm-forming abilities. We hypothesized that these two halophilic and nickel-resistant biofilm-forming bacteria can help the plants to grow under nickel-stressed environments by promoting soil aggregation as they were previously reported to resist salinity and nickel stress, as well as were found to promote plant growth under saline environments. The results revealed that under nickel stress, both bacteria promote plant growth by facilitating the formation of soil aggregates through an increase in their extra polymeric substance (EPS) production. © 2018 Science Press. All rights reserved.