Review: Organophosphonates: occurrence, synthesis and biodegradation by microorganisms

The organophosphonates are biogenic and xenobiotic compounds characterized by the presence of a stable carbon to phosphorus (C-P) bond. The C-P bond imparts upon these molecules a relative resistance to (bio)degradation and fears have been expressed over their environmental recalcitrance and possible ecotoxicity, as more than 20×103 tonnes of these compounds enter the environment annually in the U.S.A. and western Europe alone (Egli, 1988). Biodegradation of organophosphonates is generally accepted to be dependent upon the phosphate status of the cell, with biodegradation occurring only under conditions of phosphate limitation. In recent years, however, several novel bacteria capable of completely mineralizing both natural and man-made organophosphonates have been isolated. These organisms represent a departure, both at a physiological and genetic level, from the accepted consensus that organophosphonates are utilized only phosphorus sources. This review covers all aspects of our knowledge of organophosphonate metabolism over the last 50 years, concentrating on the advances made in the last 10 years.     

Carcinogenic N-nitrosamines in the diet: occurrence, formation, mechanisms and carcinogenic potential

Nitrosamines form a large group of genotoxic chemical carcinogens which occur in the human diet and other environmental media, and can be formed endogenously in the human body. N-Nitroso compounds can induce cancer in experimental animals. Some representative compounds of this class induce cancer in at least 40 different animal species including higher primates. Tumours induced in experimental animals resemble their human counterparts with respect to both morphological and biochemical properties. Extensive experimental, and some epidemiological data suggest that humans are susceptible to carcinogenesis by N-nitroso compounds and that the presence of these compounds in some foods may be regarded as an aetiological risk factor for certain human cancers including cancers of the oesophagus, stomach and nasopharynx.     

Ethyl carbamate: analytical methodology, occurrence, formation, biological activity and risk assessment

Ethyl carbamate (EC) is a genotoxic compound in vitro and in vivo, it binds covalently to DNA and is an animal carcinogen. Today, EC is mainly found as a natural trace constituent in different alcoholic beverages and in fermented food items. Data on analytical methodology and the levels of EC in different food items are summarized and the daily burden of humans is estimated. Under normal dietary habits excluding alcoholic beverages, the unavoidable daily intake is 10-20 ng/kg b.w. On the basis of the evaluation of all toxicity data and its mode of action a conventional risk assessment of EC indicates that this level represents a negligible lifetime cancer risk (less than 0.0001%). Individual habits may greatly enhance the risk. Regular drinking of table wine (500 ml/day) would increase the risk up to 5 times, regular drinking of stone-fruit distillates (20-40 ml/day) would raise the calculated hypothetical tumor risk to near 0.01%. Human exposure to carcinogenic compounds should be as low as reasonably achievable. In order to take reliable measures to reduce EC levels in beverages and foods, it is crucial to know the mode of its formation. For its natural formation the presence of ethanol is absolutely required. In stone-fruit distillates hydrogen cyanide together with photochemically active substances are crucial to form EC. The main part of EC is formed after the distillation involving photochemical reactions. In wine (and probably bread) significant EC formation seems to depend on heat treatment. While in distillates hydrogen cyanide is the most important single precursor, in wine different carbamyl compounds, mainly urea, seem to be involved in EC formation. Despite this apparent difference a common EC formation pathway is discussed for all alcoholic beverages by assuming cyanic-/isocyanic acid as an important ultimate reactant with ethanol. Some ideas are presented as to the possible course of future work.     

Recent advances in biodegradation in China: New microorganisms and pathways,biodegradation engineering,and bioenergy from pollutant biodegradation

We are facing serious environmental challenges, and environmental biotechnology is an enabling technology to reduce or eliminate pollution. In recent years, environmental pollution in China has been receiving great attention, and this paper provides an up-to-date review on progress in biodegradation research in China. This progress includes the isolation of extremophilic microorganisms for pollutant degradation in extreme conditions and the study of genes and enzymes related to biodegradation pathways. Biodegradation engineering has potential as an interesting and powerful platform, where genetic engineering, process engineering, and signal transduction engineering are applied together. In addition, pollutant treatment combined with the production of renewable sources of bioenergy by microorganisms is attractive.     

Investigation of alkane biodegradation using the microtiter plate method and correlation between biofilm formation, biosurfactant production and crude oil biodegradation

Among 25 crude oil-degrading bacteria isolated from a marine environment, four strains, which grew well on crude oil, were selected for more study. All the four isolated had maximum growth on 2.5% of crude oil and strain BC (Pseudomonas) could remove crude oil by 83%. The drop collapse method and microtiter assay show that this strain produces more biosurfactant, and its biofilm formation is higher compared to other strains. Bacterial adhesions to crude oil for strains CS-2 (Pseudomonas), BC, PG-5 (Rhodococcus) and H (Bacillus) were 30%, 46%, 10% and 1%, respectively. Therefore, strain H with a low production of biosurfactant and biofilm formation had showed the least growth on these compounds. PCR analysis of these four strains showed that all isolates had alk-B genes from group (III) alkane hydroxylase. All isolate strains could utilize cyclohexan, octane, hexadecane, octadecan and diesel fuel oil; however, the microtiter plate assay showed that strain BC had more growth, respiration and biofilm formation on octadecan.     

PHA-rubber blends: synthesis, characterization and biodegradation

Medium chain length polyhydroxyalkanoates (mcl-PHA) and different rubbers; namely natural rubber, nitrile rubber and butadiene rubber were blended at room temperature using solution blending technique. Blends constituted 5%, 10% and 15% of mcl-PHA in different rubbers. Thermogravimetric analysis of mcl-PHA showed the melting temperature of the polymer around 50 degrees C. Thermal properties of the synthesized blend were studied by Differential Scanning Calorimetry which confirmed effective blending between the polymers. Blending of mcl-PHA with natural rubber led to the synthesis of a different polymer having the melting point of 90 degrees C. Degradation studies of the blends were carried out using a soil isolate, Pseudomonas sp. 202 for 30 days. Extracellular protein concentration as well as OD660 due to the growth of Pseudomonas sp. 202 was studied. The degradation of blended plastic material, as evidenced by % weight loss after degradation and increase in the growth of organism correlated with the amount of mcl-PHA present in the sample. Growth of Pseudomonas sp. 202 resulted in 14.63%, 16.12% and 3.84% weight loss of PHA:rubber blends (natural, nitrile and butadiene rubber). Scanning electron microscopic studies after 30 days of incubation further confirmed biodegradation of the films.     

Biocatalysis, biodegradation and bioinformatics

Biocatalysis, biodegradation and bioinformatics are prominent scientific fields in industrial microbiology and biotechnology. This paper describes developments in these fields with a focus on the role of David T Gibson as a researcher and mentor. He has pioneered studies on the mechanisms by which aerobic microorganisms transform aromatic hydrocarbons. In addition, his research has served as a model for further investigations into bacterial atrazine and dichloromethane catabolism described here. Microbial catabolism research requires information on organic chemistry, microorganisms, metabolic pathways, catabolic genes, and enzymes. These information needs are now being met more comprehensively by development of the University of Minnesota Biocatalysis/Biodegradation Database. http://dragon.labmed.umn.edu/∼lynda/index.html The database is built on the ideas championed by David Gibson that a knowledge of microbial catabolic reactions should be organized in a mechanistic fashion and in a systematic format. Received 27 March 1997/ Accepted in revised form 05 June 1997     

4-oxo-2-hexenal, a mutagen formed by omega-3 fat peroxidation: occurrence, detection and adduct formation

The purpose of this review is to summarize our recent studies of a novel mutagen, 4-oxo-2-hexenal. To identify the mutagens formed in a model reaction of lipid peroxidation, linolenic acid methyl ester and hemin were reacted with dG. A 4-oxo-2-hexenal-dG adduct (dG*) was identified in the model reaction mixture. The 4-oxo-2-hexenal (4-OHE) showed mutagenic activity in the Salmonella typhimurium strains TA100 and TA104. 4-OHE reacts with DNA to form dG, dC, and 5-methyl-dC(5-Me-dC)-adducts (dG*, dC*, 5-Me-dC*) in vitro. After 4-OHE was orally administered to mice, these adducts were detected in esophageal, stomach and intestinal DNA by liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS). We also confirmed the formation of 4-OHE during the heat processing of edible vegetable oil, and during cooking. It was present at an especially high concentration in broiled saury. 4-OHE is probably generated by the oxidation of omega-3 fats. These results provide a warning to humans, who may be exposed to this mutagen. Since 4-OHE induces DNA adduct formation in experimental animal organs, further studies on the carcinogenicity of 4-OHE and the detection of 4-OHE-DNA adducts in human tissue will be required.     

Carotenoid metabolism in mammals,including man: formation,occurrence, and function of apocarotenoids: Thematic Review Series: Fat-Soluble Vitamins: Vitamin A

Vitamin A was recognized as an essential nutrient 100 years ago. In the 1930s, it became clear that dietary β-carotene was cleaved at its central double to yield vitamin A (retinal or β-apo-15′-carotenal). Thus a great deal of research has focused on the central cleavage of provitamin A carotenoids to form vitamin A (retinoids). The mechanisms of formation and the physiological role(s) of noncentral (eccentric) cleavage of both provitamin A carotenoids and nonprovitamin A carotenoids has been less clear. It is becoming apparent that the apocarotenoids exert unique biological activities themselves. These compounds are found in the diet and thus may be absorbed in the intestine, or they may form from enzymatic or nonenzymatic cleavage of the parent carotenoids. The mechanism of action of apocarotenoids in mammals is not fully worked out. However, as detailed in this review, they have profound effects on gene expression and work, at least in part, through the modulation of ligand-activated nuclear receptors. Understanding the interactions of apocarotenoids with other lipid-binding proteins, chaperones, and metabolizing enzymes will undoubtedly increase our understanding of the biological roles of these carotenoid metabolites.     

Lipoxygenases: occurrence, functions and catalysis

Lipid peroxidation is common to all biological systems, both appearing in developmentally and environmentally regulated processes. Products are hydroperoxy polyunsaturated fatty acids and metabolites derived there from collectively named oxylipins. They may either originate from chemical oxidation or are synthesized by the action of various enzymes, such as lipoxygenases (LOXes). Signalling compounds such as jasmonates, antimicrobial and antifungal compounds such as leaf aldehydes or divinyl ethers, and a plant-specific blend of volatiles including leaf alcohols are among the numerous products. Cloning of many LOXes and other key enzymes metabolizing oxylipins, as well as analyses by reverse genetic approaches and metabolic profiling revealed new insights on oxylipin functions, new reactions and the first hints on enzyme mechanisms. These aspects are reviewed with respect to function of specific LOX forms and on the development of new models on their substrate and product specificity.     

Naphthalene,phenanthrene and surfactant biodegradation

The impact of surfactants on naphthalene and phenanthrene biodegradation and vice versa after surfactant flushing were evaluated using two anionic surfactants: sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS); and two nonionic surfactants: POE (20) sorbitan monooleate (T-maz-80) and octylphenol poly(ethyleneoxy) ethanol (CA-620). Naphthalene and phenanthrene biodegradation varied differently in the presence of different surfactants. Naphthalene biodegradation was not impacted by the presence of SDS. In the presence of T-maz-80 and CA-620, naphthalene biodegradation occurred at a lower rate (0.14 d^-1 for T-maz-80 and 0.19 d^-1 for CA-620) as compared to un-amended control (0.29 d^-1). Naphthalene biodegradation was inhibited by the presence of SDBS. In the presence of SDS, phenanthrene biodegradation occurred at a lower rate (0.10 d^-1 as compared to un-amended control of 0.17 d^-1) and the presence of SDBS, CA-620 and T-maz-80 inhibited phenanthrene biodegradation. The surfactants also responded differently to the presence of naphthalene and phenanthrene. In the presence of naphthalene, SDS biodegradation was inhibited; SDBS and T-maz-80 depleted at a lower rate (0.41d^-1 and 0.12 d^-1 as compared to 0.48 d^-1 and 0.22 d^-1). In the absence of naphthalene, CA-620 was not degradable, while in the presence of naphthalene, CA-620 began to degrade at a comparatively low rate (0.12 d^-1). In the presence of phenanthrene, SDS biodegradation occurred at a lower rate (1.2 d^-1 as compared to 1.68 d^-1) and a similar trend was observed for T-maz-80. The depletion of SDBS and CA-620 did not change significantly. The choice of SDS for naphthalene-contaminated sites would not adversely affect the natural attenuation of naphthalene, in addition, naphthalene was preferentially utilized to SDS by naphthalene-acclimated microorganisms. Therefore, SDS was the best choice. T-maz-80 was also found to be usable in naphthalene-contaminated sites. For phenanthrene contaminated sites, SDS was the only choice.     

Glucoraphasatin: Chemistry, occurrence, and biological properties

Glucoraphasatin is an atypical glucosinolate mainly found in Raphanus sativus roots and sprouts. This review focuses on the chemistry, the occurrence, and the biological properties of glucoraphasatin.     

Exudate gums: occurrence,production, and applications

This paper presents a review of the industrially most relevant exudate gums: gum arabic, gum karya, and gum tragacanth. Exudate gums are obtained as the natural exudates of different tree species and exhibit unique properties in a wide variety of applications. This review covers the chemical structure, occurrence and production of the different gums. It also deals with the size and relative importance of the various players on the world market. Furthermore, it gives an overview of the main application fields of the different gums, both food and non-food.     

Plant-derived endoperoxides: structure,occurrence, and bioactivity

Phytochemistry Reviews - Endoperoxides have received widespread interest as a research topic due to its ubiquitous structure, which confers interesting biological properties. It has been...     

Germanium: environmental occurrence, importance and speciation

This review discusses the various aspects of the bio-geochemistry of germanium, and of its technological, economical and environmental importance. Despite the relatively low annual production and consumption of this semi-metal (ca. 80 metric tons/a) there are important technological applications of this element in the semiconductor, infrared optics and fibre optics/telecommunication industries. A small, but not insignificant fraction of this element is used for the production of pharmaceuticals and nutritional supplements, although its actual merits have not been fully demonstrated yet, while they are opposed to chronic toxicity of the element when being administrated at relatively high doses for an extended period of time. Neither the exact mechanism of action in the case of cancer treatment or the treatment of infectious diseases is known, nor the reason for the toxicity of inorganic species of this element. In plants, Ge can partially substitute for B in the case of boron deficiency, although deficiency symptoms are still seen with a lag period of ca. one to three weeks. In biogeochemical respect, germanium and silicon react very similar, as if Ge were a very heavy isotope of Si. Their molar ratio is typically in the order of 0.6 × 10⁻⁶, with significant deviations only where germanium is complexed and transported, e.g., by humic-rich waters. Germanium is a very conservative element in biogeochemical terms: It hardly shows involvement in any biogeochemical reaction cycles and is mainly present in the form of complexes or hydroxo-compounds of the tetravalent germanium. The only naturally occurring organogermanium compounds are mono- and dimethylgermanium which are believed to be formed by microbiological activity in continental zones containing Ge-rich minerals, and then are leached into rivers, and finally into the open sea. It becomes evident that, although very sophisticated technological uses of germanium exist, a better understanding of its biogeochemical importance, cycling and reactivity must still be developed.     

Lignocellulose biodegradation: Fundamentals and applications

Lignocelluloses are the building blocks of allplants and are ubiquitous to most regions ofour planet. Their chemical properties make it asubstrate of enormous biotechnological value.The basic chemistry of cellulose,hemicellulose, and lignin has a profound effecton lignocellulose tertiary architecture. Theseintricate associations constitute physical andchemical barriers to lignocellulose utilizationand biodegradation in natural and man-madeenvironments. Overcoming these barriers is thekey to unlocking the commercial potential oflignocellulose. Understanding lignocellulosedegradation under natural conditions forms thebasis of any lignocellulose-based application.A variety of microorganisms and mechanisms areinvolved in the complete biodegradation oflignocellulose in natural environments rangingfrom soil and rumen ecosystems to the termitehindgut. The primary objective oflignocellulose pretreatment by the variousindustries is to access the potential of thecellulose and hemicellulose encrusted by ligninwithin the lignocellulose matrix. Currentworking technologies based on the principles ofsolid-state fermentation (SSF) are brieflyreviewed. The use of unsterile lignocellulosicsfor bioremediation purposes holds promise forcost-effective environmental clean-upendeavors. Novel lignocellulose-basedapplications have found functionality intextile, biological control, and medicalresearch fields and might be exploited there inthe near future. Ultimately, lignocellulosewill probably accompany man to his voyages intospace for interest in this field isintensifying. Therefore, proper management oflignocellulose biodegradation and utilizationcan serve to improve the quality of theenvironment, further man's understanding of theuniverse, and ultimately change local economiesand communities.