Bioremediation of PAHs and VOCs: Advances in clay mineral–microbial interaction

Bioremediation is an effective strategy for cleaning up organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Advanced bioremediation implies that biotic agents are more efficient in degrading the contaminants completely. Bioremediation by microbial degradation is often employed and to make this process efficient, natural and cost-effective materials can serve as supportive matrices. Clay/modified clay minerals are effective adsorbents of PAHs/VOCs, and readily available substrate and habitat for microorganisms in the natural soil and sediment. However, the mechanism underpinning clay-mediated biodegradation of organic compounds is often unclear, and this requires critical investigation. This review describes the role of clay/modified clay minerals in hydrocarbon bioremediation through interaction with microbial agents in specific scenarios. The vision is on a faster, more efficient and cost-effective bioremediation technique using clay-based products. This review also proposes future research directions in the field of clay modulated microbial degradation of hydrocarbons.     

Biological diversity of nitrile-metabolizing bacteria in soils of the Perm region affected by human activities

The diversity of bacteria metabolizing nitriles of carbonic acids was studied in soils of the Perm region affected by human activities. Effective methods for selective isolation of cultures possessing the nitrile hydratase and nitrilase activities were developed. Most microorganisms capable of utilizing nitriles were Grampositive Nocardia-like bacteria of the genus Rhodococcus. Isolates with a detectable nitrilase activity were also represented by Gram-negative forms (Gram-negative aerobic/microaerophilic bacilli and cocci of the genera Pseudomonas, Azomonas, Azotobacter, and Acidovorax). Two enzyme systems for nitrile hydrolysis were found in 27% of cultures. The nitrile hydratase and nitrilase activities of the studied strains exceeded these enzymatic activities in bacteria isolated from native soils, which indicates that natural selection of saprophytic microflora occurs in chemically altered soils.     

Earthworm assisted bioremediation of organic contaminants

Due to their biological, chemical and physical actions, earthworms can be directly employed within bioremediation strategies to promote biodegradation of organic contaminants. Earthworms have been shown to aerate and bioturbate soils and improve their nutritional status and fertility, which are variables known to limit bioremediation. Earthworms have also been shown to retard the binding of organic contaminants to soils, release previously soil-bound contaminants for subsequent degradation, and promote and disperse organic contaminant degrading microorganisms. This review discusses these earthworm actions upon the soil environment and how they might influence the fate and behaviour of soil associated organic contaminants, subsequently improving bioremediation potential. The latter part of this review considers organic compounds in the following order: agrochemicals, petroleum and crude oil hydrocarbons, PAHs and PCBs.     

A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds comprised of two or more fused benzene rings arranged in various configurations. PAHs are widespread environmental contaminants formed as a result of incomplete combustion of organic materials such as fossil fuels. The occurrence of PAHs in ambient air is an increasing concern because of their carcinogenicity and mutagenicity. Although emissions and allowable concentrations of PAHs in air are now regulated, the health risk posed by PAH exposure suggests a continuing need for their control through air quality management. In light of the environmental significance of PAH exposure, this review offers an overview of PAH properties, fates, transformations, human exposure, and health effects (acute and chronic) associated with their emission to the atmosphere. Biomarkers of PAH exposure and their significance are also discussed.     

Mechanistic aspects regarding the direct aqueous environmental photochemistry of phenol and its simple halogenated derivatives. A review

We have reviewed the mechanistic aspects regarding the direct aqueous phase environmental photochemistry of phenol and its simple halogenated derivatives. These compounds are important industrial and natural products, are ubiquitous in aquatic systems, and their acute and chronic toxicity makes their environmental fate of interest. Work over the past two decades has unified the photochemistry of phenol and its simple halogenated derivatives. In general, three photochemical pathways dominate in aqueous solution depending on the nature of the substrate: (1) photoionization, (2) photochemical aryl-halogen bond homolysis, and (3) photochemical aryl-halogen bond heterolysis. Photoionization typically results in an array of biaryl radical coupling products which are only relevant for highly concentrated waste streams. Photolytic aryl-halogen bond homolysis will primarily give photoreduction products where reducing agents such as dissolved organic matter or reduced metal cations are present, and radical coupling products in highly concentrated waste streams. The 2- and 4-substituted halophenols may undergo photochemical aryl-halogen bond heterolysis upon irradiation to give an aryl cation. The aryl cation can be attacked by water to give the corresponding hydroxylated derivative, or may deprotonate to generate alpha- and gamma-ketocarbenes, respectively. Following their formation, the singlet alpha-ketocarbenes may undergo Wolff rearrangements to cyclopentadiene-ketenes that are subsequently hydrolyzed to cyclopentadiene carboxylic acids. The triplet alpha- and gamma-ketocarbenes are attacked by oxygen and hydrolyzed to give benzoquinones, directly hydrolyzed to yield hydroquinones, reduced to give phenols, or could take part in coupling reactions in highly concentrated waste streams to give dimers and hydroxybiaryl complexes. Additional studies in natural water samples are required to assess the relative importance of these direct irradiation mechanisms relative to indirect photolysis and other abiotic and biotic degradation and environmental partitioning pathways across the continuum of marine, freshwater, and wastewater biogeochemical signatures.     

A review of the significance and formation of chlorinated N-organic compounds in water supplies including preliminary studies on the chlorination of alanine,tryptophan, tyrosine,cytosine, and syringic acid

Nitrogenous organic compounds are of environmental significance because of their potential as both trihalomethane (THM) and nonpurgeable organic halide (NPOX) precursors. They additionally lead to falsely positive tests for free available chlorine (FAC) and are components in the reaction of chlorine to form dihaloacetonitriles (DHANs). A large number of naturally occurring nitrogenous compounds additionally react readily with aqueous chlorine exerting significant chlorine demand. Such reactions generally involve the substitution of chlorine for hydrogen on a nitrogen atom. Additionally, N-chloroorganic materials may be produced even when the precursor concentration is low owing to the rapid specific rate of formation. While previous attention has been largely focused on nonpolar chlorinated organic contaminants such as THMs, the wide distribution of N-organic compounds in water, as well as their general reactivity towards aqueous chlorine, warrant further attention and study to this group of materials. Preliminary studies on the chlorination of several N-organic compounds at a few chlorine-to-compound molar ratios at pH 7 and 4.7 over several reaction intervals are presented. NPOX formation was quite rapid and comprised the greatest proportion of the total organic halide formed for the conditions studied.     

Determination of potentially bioaccumulating complex mixtures of organochlorine compounds in wastewater: a review

Organic chlorine compounds can be persistent environmental contaminants and may be accumulated through the food chain to the aquatic organisms, to fish and humans, depending basically on their hydrophobic properties. Consequently, there is an interest to measure these organic compounds from both the scientific and regulatory communities. The analytical essays have been improved for measuring specific organic chlorine compounds that present the most toxicological potential (polychlorinated biphenyls [PCBs], certain pesticides and dioxins), although they are tedious and time-consuming procedures. The existing tests to measure adsorbable organic halogens (AOX) or extractable organic halogens (EOX) do not distinguish the more hydrophobic organic chlorine matter. The intention of this paper is to make a review of the existing methods to measure the potentially bioaccumulating organochlorine compounds (OCs) from wastewater and propose a methodology to a standardisation procedure for complex mixtures of OCs in wastewater, such as pulp mill effluents. A new method has been proposed for determining the most hydrophobic part of the extractable organic halogens (EOX(fob)), the lowest reported value is 0.6 microg/l, expressed as chloride, and the relative standard deviation at 20 microg/l is 7% on laboratory samples and 30% on real effluents. This new procedure could be a valuable tool to complement environmental risk assessment studies of wastewater discharges.     

An overview of commercially used brominated flame retardants,their applications,their use patterns in different countries/regions and possible modes of release

Brominated flame retardants (BFRs) are used in a variety of consumer products and several of those are produced in large quantities. These compounds have been detected in environmental samples, which can be attributed to the anthropogenic uses of these compounds. Brominated flame retardants are produced via direct bromination of organic molecules or via addition of bromine to alkenes; hence, an overview of the production and usage of bromine over the past three decades is covered. Production, application, and environmental occurrence of high production brominated flame retardants including Tetrabromobisphenol A, polybrominated biphenyls, Penta-, Octa-, Deca-brominated diphenyl ether (oxide) formulation and hexabromocyclododecane are discussed.     

Preliminary exploration of the relationships between soil characteristics and PAH desorption and biodegradation

Desorption and biodegradation of pyrene (PYR) were investigated and their relationships to soil characteristics were addressed. The results indicated that maximum achievable desorption was 30.2, 10.4, and 1.0 mg/kg for soils that had 1.7, 2.2, and 4.4 wt.% of expandable clays (smectite and vermiculite), respectively. Neither dissolved organic matter (DOM) nor total clay amounts made a good prediction of the desorption trend. Subsequently, the ease of desorption facilitated a faster aqueous biodegradation rate. The slowest aqueous biodegradation rate, 0.02 l/h, was achieved for the soil system that had the greatest amount of expandable clays, whereas the soil containing 1.7% expandable clays only achieved 0.73 l/h. The soil with 2.2% expandable clays depicted 0.41 l/h of aqueous biodegradation rate. A good linear correlation was obtained between maximum achievable desorption and aqueous biodegradation rate (R(2)=0.92). Soil analysis revealed that the total (soil+water) biodegradation reached was 65%, 78.3%, and 81.8% of the initial concentration (100 mg/kg) for the sandy clay loam (Colombian), sandy loam (Ohio), and silty loam (New Mexico) soils, respectively. This biodegradation extent was also in good agreement of expandable clay amount. Although aqueous PYR bioavailability was limited due to the strong association with the expandable clays, microbial movement and adhesion to those clays seemed to result in a great extent of the soil-phase biodegradation.     

Playing with fire: the global threat presented by brominated flame retardants justifies urgent substitution

Few would now deny that the use of organobromine compounds to achieve fire retardancy in a diverse array of products and materials has led to contamination of the ecosphere on a widespread scale. This environmental prevalence and persistence of the brominated flame retardants, coupled with growing evidence of their potential for harm, present all too familiar parallels with the previous generation of persistent organic pollutants. Indeed, given the intrinsic properties of these brominated chemicals, the nature and extent of the current problem could well have been predicted in advance. The question is then whether we are prepared to let history repeat itself once more or to take precautionary action now to switch to more sustainable alternatives. The choice facing society is not between brominated flame retardants and unsafe products, but between fire safety leading to global contamination or fire safety achieved in less polluting ways. If we look beyond options for simple chemical-for-chemical substitution to alternative materials and designs, many of the solutions are already available. The remainder could undoubtedly be developed given the incentives to do so. However, a strong and clear policy approach, backed by legislative phase-outs within specified (and challenging) timeframes, will be necessary to break our current dependency on organobromine chemistry. This paper presents the justification for such an approach, reviews those initiatives already underway to replace brominated flame retardants and identifies pathways to the use of more sustainable products in the service of society.     

Pharmaceuticals and personal care products (PPCPs): A review on environmental contamination in China

Pharmaceuticals and personal care products (PPCPs) which contain diverse organic groups, such as antibiotics, hormones, antimicrobial agents, synthetic musks, etc., have raised significant concerns in recently years for their persistent input and potential threat to ecological environment and human health. China is a large country with high production and consumption of PPCPs for its economic development and population growth in recent years. This may result in PPCP contamination in different environmental media of China. This review summarizes the current contamination status of different environment media, including sewage, surface water, sludge, sediments, soil, and wild animals, in China by PPCPs. The human body burden and adverse effects derived from PPCPs are also evaluated. Based on this review, it has been concluded that more contamination information of aquatic environment and wildlife as well as human body burden of PPCPs in different areas of China is urgent. Studies about their environmental behavior and control technologies need to be conducted, and acute and chronic toxicities of different PPCP groups should be investigated for assessing their potential ecological and health risks.     

Biodegradation of low-density polyethylene (LDPE) using the mixed culture of Aspergillus carbonarius and A. fumigates

Low-density polyethylene (LDPE) possesses various applications in several industries owing to its durability, low-cost, and many mechano-thermal properties. Unfortunately, LDPE waste creates an environmental threat. The level of biodegradation of black LDPE sheets with fungi isolated from different landfills sites in Sharqiyah Governorate, Egypt, was evaluated. LDPE sheets, the only source of carbon, along with minimal salt medium were incubated on a rotary shaker at 30 °C and 120 rpm for 16 weeks. Aspergillus carbonarius MH 856457.1 and A. fumigatus MF 276893 confirmed to be good candidates for LDPE biodegradation. A mixed culture of two strains showed the excellent weight loss% of sheets as compared to single isolate. Further efforts to improve the degrading capacity through physical and chemical treatments were performed. The biodegradation was significantly stimulated by 39.1% (thermal treatment), 17.76% (HNO₃ treatment), and 5.79% (Gamma-irradiation treatment). Laccases and manganese peroxidases activities were assayed. LDPE biodegradation was analyzed by scanning electronic microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and gas chromatography–mass spectrometry (GC–MS). FTIR spectra showed the appearance of new functional groups assigned to hydrocarbon biodegradation and confirmed the role of manganese peroxidase in process. The changes in the FTIR spectra of the mixed culture biomass before and after the biodegradation (Δ73 cm^?1) and the surface changes in the biodegraded LDPE (as indicated from SEM) confirmed the depolymerization of LDPE. From GC–MS analysis, the plasticizers bis(2-ethylhexyl) phthalate, Diisssctyl phthalate, 1,2-benzenedicarboxylic acid diisooctyl ester, and tributyl acetylcitrate completely biodegraded. Moreover, several antioxidants, antimicrobial, and anticancer compounds, and methyl esters of fatty acids were produced.

     

Measurement of organic compound emission using small test chambers

Organic compounds emitted from a variety of indoor materials have been measured using small (166 L) environmental test chambers. The paper discusses: a) factors to be considered in small chamber testing; b) parameters to be controlled; c) the types of results obtained. The following types of materials have been tested: adhesives, caulks, pressed wood products, floor waxes, paints, and solid insecticides. Selected data are presented. For each material, chamber concentrations of organic compounds have been determined for a range of environmental conditions (e.g., air exchange rate, temperature and relative humidity). Emission rates for individual organic compounds, as well as total measured organics, were calculated. The effects of environmental variables on emission rates have been evaluated. Models are used to evaluate the effect of chamber walls and concentration on emission rates.     

Organoarsenicals in poultry litter: Detection,fate, and toxicity

Arsenic contamination in groundwater has endangered the health and safety of millions of people around the world. One less studied mechanism for arsenic introduction into the environment is the use of organoarsenicals in animal feed. Four organoarsenicals are commonly employed as feed additives: arsanilic acid, carbarsone, nitarsone, and roxarsone. Organoarsenicals are composed of a phenylarsonic acid molecule with substituted functional groups. This review documents the use of organoarsenicals in the poultry industry, reports analytical methods available for quantifying organic arsenic, discusses the fate and transport of organoarsenicals in environmental systems, and identifies toxicological concerns associated with these chemicals. In reviewing the literature on organoarsenicals, several research needs were highlighted: advanced analytical instrumentation that allows for identification and quantification of organoarsenical degradation products; a greater research emphasis on arsanilic acid, carbarsone, and nitarsone; identification of degradation pathways, products, and kinetics; and testing/development of agricultural wastewater and solid treatment technologies for organoarsenical-laden waste.     

Natural and man-made organobromine compounds in marine biota from Central Norway

Brominated organic pollutants were found in selected samples of mollusk tissue, fish liver, as well as in the eggs and livers of shag from three sites in Central Norway. More than 80 organobromines were identified owing to the defined isotope ratio acquired by GC/ECNI-MS. However, only a few peaks could be assigned to anthropogenic brominated flame retardants (polybrominated diphenyl ethers). Most of the organobromine compounds detected were unknown or halogenated natural products. The known halogenated natural products MHC-1 and TBA were abundant in all samples and usually between equally abundant, and up to 50 fold more concentrated than the major polybrominated diphenyl ether congener BDE 47. The halogenated natural products BC-2 (2-MeO-BDE 68) and BC-3 (6'-MeO-BDE 47), were on level with BDE 100 which was the second most abundant BDE congener in many samples. The previously identified natural polybrominated hexahydroxanthene derivatives (PBHDs) were detected for the first time in bird eggs. Being major contaminants in bird eggs, PBHDs were only present at low levels in bird liver from nestlings originating from the same clutch. Such differences were detected for several other major contaminants. One unknown tetrabromo compound particularly abundant in mussels from Munkholmen was studied by GC/MS and the molecular ion was detected at m/z 446. The abundance of the most important unknown compounds did not correlate with BDEs and they most likely represent halogenated natural products. This study supports that halogenated natural products have to be treated as serious contaminants of marine coastal waters. Our data suggest that their abundance is highest in habitats along the shoreline. Thorough examination of these compounds in environmental samples is an important task.     

Worldwide occurrence and effects of antifouling paint booster biocides in the aquatic environment: a review

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin (TBT) in 1987. Replacement products are generally based on copper metal oxides and organic biocides. This ban has led to an increase in alternative coating products containing the above biocides. The most commonly used biocides in antifouling paints are: Irgarol 1051, diuron, Sea-nine 211, dichlofluanid, chlorothalonil, zinc pyrithione, TCMS (2,3,3,6-tetrachloro-4-methylsulfonyl) pyridine, TCMTB [2-(thiocyanomethylthio) benzothiazole], and zineb. Since 1993, several studies have demonstrated the presence of these biocides in European coastal environment as a result of their increased use. More recently, the presence of these biocides was also revealed in waters from Japan, United States, Singapore, Australia and Bermuda. This paper reviews the currently available data on the occurrence of these biocides in the aquatic environment. Some data dealing with the environmental fate, partitioning, behaviour and risk assessment of antifouling paint booster biocides are also reported in order to discuss the detected levels of contamination.     

Metal bioremediation through growing cells

Heavy-metal pollution represents an important environmental problem due to the toxic effects of metals, and their accumulation throughout the food chain leads to serious ecological and health problems. Metal remediation through common physico-chemical techniques is expensive and unsuitable in case of voluminous effluents containing complexing organic matter and low metal contamination. Biotechnological approaches that are designed to cover such niches have, therefore, received great deal of attention in the recent years. Biosorption studies involving low-cost and often dead/pretreated biomass have dominated the literature and, subsequently, extensive reviews focusing on equilibrium and kinetics of metal biosorption have also come up. However, the low binding capacity of biomass for certain recalcitrant metals such as Ni and failure to effectively remove metals from real industrial effluents due to presence of organic or inorganic ligands limit this approach. At times, when pure biosorptive metal removal is not feasible, application of a judicious consortium of growing metal-resistant cells can ensure better removal through a combination of bioprecipitation, biosorption and continuous metabolic uptake of metals after physical adsorption. Such approach may lead to simultaneous removal of toxic metals, organic loads and other inorganic impurities, as well as allow optimization through development of resistant species. However, sensitivity of living cells to extremes of pH or high metal concentration and need to furnish metabolic energy are some of the major constraints of employing growing cells for bioremediation. The efforts to meet such challenges via isolation of metal-resistant bacterial/fungal strains and exploitation of organic wastes as carbon substrates have began. Recent studies show that the strains (bacteria, yeast and fungi) isolated from contaminated sites possess excellent capability of metal scavenging. Some bacterial strains possess high tolerance to various metals and may be potential candidates for their simultaneous removal from wastes. Evidently, the stage has already been set for the application of metal-resistant growing microbial cells for metal harvesting. This review focuses on the applicability of growing bacterial/fungal/algal cells for metal removal and the efforts directed towards cell/process development to make this option technically/economically viable for the comprehensive treatment of metal-rich effluents.     

Energy analysis of algae-to-biofuel production chains integrated with a combined heat and power plant

ABSTRACT

This study examines the energy and mass balances of algae cultivation and different post-processing pathways. Flue gases and excess heat from a combined heat and power (CHP) plant are used in algae cultivation, with nutrients from municipal wastewater. In the studied pathways, algae are cultivated in open ponds and photobioreactors with or without artificial lighting. Algal mass is used for methane, biodiesel or ethanol production, or it is combusted in a boiler. Results show that in most process pathways energy output exceeds the energy consumption in processing, and the energy returns are approximately twice as large as the electricity input. A large fraction of input energy is low-temperature heat, while the products have a higher value. Energy outputs from different pathways are similar, but heat and electricity consumption in processing vary significantly. Supercritical water gasification pathway is identified as a possible future option, whereas lipid extraction pathways are suggested to be the most likely candidates for industrial scale operations.     

Screening of household products for the emission of volatile organic compounds

10 household products, eight waxes or polishes, and two detergents have been screened by a headspace technique for the emission of volatile organic compounds (VOC). Using Tenax sampling and analysis by combined gas chromatography-mass spectrometry (GC-MS) more than 80 single compounds or groups of isomers have been identified, and semiquantitative data on the initial emission rates (emission rate immediately after application) have been obtained. Products fall into two groups: those containing water as a main (80 to 90%) constituent and those without water. The initial emission rate of the first group ranged from 0.2 to 2 μg cm⁻²min⁻¹, whereas the second group had higher emission rates of up to 430 μg cm⁻²min⁻¹. Products of the second group emit essentially hydrocarbons (alkanes, alkenes, and terpenes), whereas most products of the first group emit oxygenated compounds including terpene alcohols and their acetates, aliphatic alcohols and esters, and alkoxy-alcohols.