Biodegradation kinetics of selected brominated flame retardants in aerobic and anaerobic soil

The purpose of the present study was to investigate the biodegradation kinetics in aerobic and anaerobic soil of the following brominated flame retardants: 2,4,4′-tribromodiphenyl ether (BDE 28), decabromodiphenyl ether (BDE 209), tetrabromobisphenol A (TBBPA), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), 2,4,6-tribromophenol (246BrPh), and hexabromobenzene (HxBrBz). For comparison, the biodegradation of the chlorinated compounds 2,4,4′-trichlorodiphenyl ether (CDE 28), 2,4,6-trichlorophenol (246ClPh), hexachlorobenzene (HxClBz), and 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB 153) was also assessed. In aerobic soil, BDE 209 showed no significant degradation during the test period, but concentrations of the other BFRs declined, with half-lives decreasing in the following order: BDE 28 > TBBPA > TBECH > HxBrBz > 246BrPh. Declines in almost the same order were observed in anaerobic soil: BDE 28, BDE 209 > TBBPA > HxBrBz > TBECH >246BrPh.     

Abiotic reduction reactions of anthropogenic organic chemicals in anaerobic systems: A critical review

This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several difficulties (both semantic and experimental) that recur in the studies reviewed are discussed. The subtle effects of various sterilization techniques on extracellular biochemicals and complex chemical reducing agents in sediment have stifled attempts to separate abiotic from biological degradation reactions. The characterization of redox conditions in a natural system is still problematic since measured redox potential is not adequate. Suggestions for future research toward a process-level understanding of abiotic chemical reductions are made.     

焦化厂A/O出水中的有机污染物分析

采用色谱－质谱（GC／MS）联用仪分析和鉴定了上海宝钢焦化厂A／O生化阶段出水的有机污染物组成,共检出各类有机污染物70多种。结合焦化废水专用混凝剂的混凝处理实验结果,指出了各类有机污染物的去除情况。     

Estimating biotransformation rate constants of organic chemicals from modeled and measured elimination rates.

In this study, biotransformation rate constants are estimated for a large set of organic compounds. Biotransformation (km) is considered part of the total elimination, further consisting of physico-chemical elimination to water (kw), depuration by feces (kf) and growth dilution (gamma). Existing models are used to estimate kw and kf, and gamma. The difference between measured elimination rate constants and the sum of predicted elimination rate constants for water, feces and growth indicates the ration of biotransformation in the total elimination. In all examined animal classes, polycyclic aromatic hydrocarbons seem to be metabolized at an intermediate rate. Because of the relative low hydrophobicity of some of the studied compounds, their physico-chemical elimination rate constant is relatively high, and the relative contribution of metabolism to total elimination of these compounds is therefore relatively low. Fish seem to be capable of metabolizing chlorodibenzo-p-dioxins and -furans, DDT, chloroanilines and phenol.     

Reaction rates and intermediates of chlorinated organic compounds in water and soil

Degradation reactions of thirteen chlorinated organic compounds were investigated in a water system and a water-soil system. Three compounds were degraded following the first order rate equation regardless of pH, and five compounds were degraded following the second order rate equation with a concentration of hydroxide ion in alkaline solution.The reaction rate constants and the activation energies of the reactions were obtained, and the intermediates were determined quantitatively for the eight compounds.From the result of the degradation of 1,1,1-trichloroethane in the water-soil system, it was found that 1,1,1 trichloroethane did not react on the soil surface and only reacted in the water phase.     

Rate of microbial degradation of high concentrations of α-hexachlorocyclohexane in soil under aerobic and anaerobic conditions

A case study was carried out to determine the bio-degradability of α-HCH in waste dumps polluted with HCH-isomers. Polluted soil was homogenized through a 2 mm sieve. The degradation of α-HCH (5300 mg kg^?1) occurred under anaerobic as well as under aerobic conditions; the concentration decreased in 20 weeks with 35% and 55% respectively. Addition of glucose, glutamic acid and peptone to the polluted soil hardly affected the degradation rate of α-HCH.     

Formation and release of residues of the 14C-labelled herbicide isoproturon and its metabolites bound in model polymers and in soil

The humic monomer catechol was reacted with (14)C-isoproturon and some of its metabolites, including (14)C-4-isopropylaniline, in aqueous solution under a stream of oxygen. Only in the case of (14)C-4-isopropylaniline, incorporation in oligomers, in fulvic acid-like polymers, and in humic acid-like polymers by covalent bonds was observed. The main oligomer was identified by mass spectrometry as a trimer, 4,5-bis-(4-isopropylphenylamino)-3,5-cyclohexadiene-1,2-dione. Biomineralization of (14)C-compounds to (14)CO(2) in a loamy soil and release of (14)C from soil columns into percolate water decreased in the order: free isoproturon >free 4-isopropylaniline>fulvic acid-like polymers>trimer>humic acid-like polymers. In soil columns, a small but measurable migration of (14)C from polymers from upper to deeper soil layers could be detected; most of this (14)C was bound again in a non-extractable form. It is concluded that aniline-derived pesticides bound in soil by covalent binding may not be fully undegradable, nor fully immobile.     

Mineralization,metabolism and formation of non-extractable residues of 14C-labelled organic contaminants during pilot-scale composting of municipal biowaste

Use of municipal biowaste for composting instead of its disposal has become a major source of concern as regards contamination by hazardous substances. To elucidate the hazard potential of compost application, municipal biowaste was amended with 14C-labelled model substances (pyrene, simazine) and incubated in a pilot-scale composting simulation system. A mass balance incorporating the mineralization, metabolism and sorption of the two model substances was established over a period of 370 days. The results are quite different for the two chemicals, reflecting their intrinsic properties: more than 60% of the applied 14C-simazine resulted in non-extractable residues (NER). Silylation experiments indicated that the formation of NER from simazine and its metabolites was due to both physical entrapment in the matrix and chemical binding. The mineralization and formation of NER represented the major pathways of disappearance for pyrene during one year of composting, accounting for 60 and 26% of initially applied 14C-activity, respectively. Mineralization occurred delayed after the thermophilic phase. As regards remobilization, release of pyrene from NER during composting could be excluded, whereas simazine, data were inconclusive in this respect.     

污水污泥发酵制园林营养土的好氧-厌氧交替方式控制研究

为使污水污泥发酵后制成的园林营养土符合无害化、营养化、腐殖化的要求,通过好氧-厌氧交替试验,考察了不同通风方式、好氧-厌氧交替方式下的大肠菌群数量、发酵温度、有效氮、有效磷、腐殖质等的变化,以确定交替试验的最佳条件.结果表明,污水污泥发酵制园林营养土较佳的通风方式为:通气量1.4～2.8 m3/(h·t)、通气5 mi...     

餐厨垃圾湿式厌氧消化最优有机负荷及失稳指标

为探究餐厨垃圾湿式厌氧消化最佳有机负荷及失稳预警指标,在(36±1) ℃单相连续搅拌条件下进行有机负荷(OLR)梯度实验。通过理论及数学分析确定90%含水率餐厨垃圾湿式厌氧消化的最佳OLR和失稳指标。当OLR（以VS计）为2.94 g?(L?d)-1时,挥发性固体去除率、甲烷产率、容积沼气产率分别为78%、0.58 L?g-1VS、2.99 L?(L?d)-1,此时厌氧反应器达到最佳运行状态。一定浓度的游离氨(FAN)会抑制微生物活性,触发挥发性脂肪酸(VFA)的积累,造成容积沼气产率降低,第36天,当OLR增至3.21 g?(L?d)-1时,FAN浓度升至区域峰值207 mg?L-1,但随后骤降35.9%（39 d）,分别造成VFA和挥发性脂肪酸浓度与碳酸氢盐碱度的比值(VFA/TA)从第37天的1 897 mg?L-1、0.22升高至第47天的4 755 mg?L-1、0.73,系统进入抑制稳定状态,最终导致容积沼气产率从第47天的2.66 L?(L?d)-1降至第48天的1.88 L?(L?d)-1,系统恶化。协同分析表明,当VFA和VFA/TA分别达到2 500 mg?L-1和0.35并出现持续上升的现象时,能提前7～8 d对90%含水率餐厨垃圾湿式厌氧消化系统的失稳提出预警。     

Influence of methanol on retention of hydrophobic organic chemicals in soil leaching column chromatography

The influence of methanol in methanol-water mixed eluents on the capacity factor (k'), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Short-term exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - S(phi), could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w) had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process.     

Enantioselective biodegradation of mecoprop in aerobic and anaerobic microcosms

Natural attenuation of mecoprop has been studied by determining changes in enantiomeric fraction in different redox environments down gradient from a landfill in the Lincolnshire limestone. Such changes could be due to differential metabolism of the enantiomers, or enantiomeric inversion. In order to confirm the processes occurring in the field, microcosm experiments were undertaken using limestone acclimatised in different redox zones. No biodegradation was observed in the methanogenic, sulphate-reducing or iron-reducing microcosms. In the nitrate-reducing microcosm (S)-mecoprop did not degrade but (R)-mecoprop degraded with zero order kinetics at 0.65 mg l(-1)day(-1) to produce a stoichiometric equivalent amount of 4-chloro-2-methylphenol. This metabolite only degraded when the (R)-mecoprop disappeared. In aerobic conditions (S)- and (R)-mecoprop degraded with zero order kinetics at rates of 1.90 and 1.32 mg l(-1)day(-1) respectively. The addition of nitrate to dormant iron-reducing microcosms devoid of nitrate stimulated anaerobic degradation of (R)-mecoprop after a lag period of about 20 days and was associated with the production of 4-chloro-2-methylphenol. Nitrate addition to sulphate-reducing/methanogenic microcosms did not stimulate mecoprop degradation. However, the added nitrate was completely utilised in oxidising sulphide to sulphate. There was no evidence for enantiomeric inversion. The study reveals new evidence for fast enantioselective degradation of (R)-mecoprop under nitrate-reducing conditions.     

Biodegradation of polylactide in aerobic and anaerobic thermophilic conditions

Biodegradable polymers are designed to resist a number of environmental factors during use, but to be biodegradable under disposal conditions. The biodegradation of polylactide (PLLA) was studied at different elevated temperatures in both aerobic and anaerobic, aquatic and solid state conditions. In the aerobic aquatic headspace test the mineralisation of PLLA was very slow at room temperature, but faster under thermophilic conditions. The clear effect of temperature on the biodegradability of PLLA in the aquatic tests indicates that its polymer structure has to be hydrolysed before microorganisms can utilise it as a nutrient source. At similar elevated temperatures, the biodegradation of PLLA was much faster in anaerobic solid state conditions than in aerobic aquatic conditions. The behaviour of PLLA in the natural composting process was similar to that in the aquatic biodegradation tests, biodegradation starting only after the beginning of the thermophilic phase. These results indicate that PLLA can be considered as a compostable material, being stable during use at mesophilic temperatures, but degrading rapidly during waste disposal in compost or anaerobic treatment facilities.     

Environmental hazard profile of organic chemicals: An experimental method for the assessment of the behaviour of organic chemicals in the ecosphere by means of simple laboratory tests with 14C labelled chemicals

The concept of “Environmental Hazard Profile” developed at this institute has been tested with 100 ¹⁴C-labelled organic compounds. Concentration factors in activated sludge, in algae and fish were determined. The microbial degradation of the chemicals to CO₂ in activated sludge and the decomposition to CO₂ under artificial light were determined. Ranking of compounds is given in the order of falling concentration factors and accumulation in rats respectively, and decreasing rates of decomposition. Relationship between chemical structure and accumulative and degradative behaviours is demonstrated using some selected groups of chemicals, such as benzenes, phenols, biphenyls and polyaromatic hydrocarbons. Correlations between the octanol/water partition coefficient, concentration factors and rates of decomposition could be established. Evaluation of test compounds was possible using hazard profiles obtained by the sum of single test results.     

An integrated anaerobic/aerobic bioprocess for the remediation of chlorinated phenol-contaminated soil and groundwater.

An investigation of biodegradation of chlorinated phenol in an anaerobic/aerobic bioprocess environment was made. The reactor configuration used consisted of linked anaerobic and aerobic reactors, which served as a model for a proposed bioremediation strategy. The proposed strategy was studied in two reactors before linkage. In the anaerobic compartment, the transformation of the model contaminant, 2,4,6-trichlorophenol (2,4,6-TCP), to lesser-chlorinated metabolites was shown to occur during reductive dechlorination under sulfate-reducing conditions. The consortium was also shown to desorb and mobilize 2,4,6-TCP in soils. This was followed, in the aerobic compartment, by biodegradation of the pollutant and metabolites, 2,4-dichlorophenol, 4-chlorophenol, and phenol, by immobilized white-rot fungi. The integrated process achieved elimination of the compound by more than 99% through fungal degradation of metabolites produced in the dechlorination stage. pH correction to the anaerobic reactor was found to be necessary because acidic effluent from the fungal reactor inhibited sulfate reduction and dechlorination.     

Effect of ozone pretreatment on characteristics of dissolved organic matter formed in aerobic and anaerobic digestion of waste-activated sludge

Environmental Science and Pollution Research - The characteristics of dissolved organic matter (DOM) formed in aerobic and anaerobic digestion of waste-activated sludge (WAS) after ozone...     

Mineralisation studies of 14C-labelled metsulfuron-methyl, tribenuron-methyl, chlorsulfuron and thifensulfuron-methyl in one Danish soil and groundwater sediment profile.

Bacterial mineralisation of four sulfonylurea herbicides at 20 microg kg(-1) in a sandy soil from nine different depths in a sandy soil horizon (5-780 cm) was investigated in laboratory studies. Metsulfuron-methyl, chlorsulfuron, and tribenuron-methyl were 14C-labelled in the sulfonamide ring, while thifensulfuron-methyl was labelled in the thiophene ring. The highest mineralised amount in 126 days was observed for metsulfuron-methyl (40%) followed by tribenuron-methyl (25%), and thifensulfuron-methyl (11%). Chlorsulfuron showed low mineralisation in all the soils tested (<4%). Mineralisation of the herbicides metsulfuron-methyl and tribenuron-methyl varied according to soil depth (upper profile: 5-70 cm, and lower profile: 165-780 cm) and were proven faster in soil taken from depths 5-7 and 30-35 cm, and slower in depths 45-50 and 70-75 cm. Mineralisation was absent in the lower profile (165-780 cm). As an indicator of microbial activity bacterial counts were taken at the experimental start; these counts grouped in three levels: highest in the surface layer (5-7 cm), slightly lower in the depths 30-75 cm, and lowest in the lower profile (165-780 cm). Residual concentrations of metsulfuron-methyl correlated to the accumulated amount mineralised, with high residual concentrations in soil showing low mineralisation. Also chlorsulfuron showed high residual concentrations with increasing depth in the upper profile, but the relatively high dissipation at 30-35 cm and lower one at 45-50 cm could not be related with the lack of mineralisation. This shows that hydrolysis occurs, but mineralisation of the chloro-substituted sulfonamide is restricted. Tribenuron-methyl and thifensulfuron-methyl could not be detected due to interference with other compounds.     

Evaluation of a serum bottle technique for assessing the anaerobic biodegradability of organic chemicals under methanogenic conditions

The serum bottle method of Shelton and Tiedje (1984), for assessing the potential of an organic chemical to undergo anaerobic biodegradation, was evaluated using U.K. primary digesting sludges. The method was modified by using the sludge at a known solids content and employing sterile (autoclaved) controls to correct for abiotic gas production. Gas production was measured with a compact hand-held pressure meter, which represented an improvement over previously described techniques. Results obtained confirmed the reliability and precision of this type of simple, screening test for assessing anaerobic biodegradability. However, the test is only applicable to low-sulphate, methanogenic environments and evidence is presented of interference from sulphate-reducing bacteria (SRB) when testing sulphate-containing chemicals.     

Degradation of toxaphene in water during anaerobic and aerobic conditions

The degradation of technical toxaphene in water with two kinds of bioreactors operating in sequence was studied. One packed bed reactor was filled with Poraver (foam glass particles) running at anaerobic conditions and one suspended carrier biofilm reactor working aerobically. Chemical oxygen demand (COD), chloride, sulphate, pH, dissolved oxygen, total toxaphene and specific toxaphene isomers were measured. After 6 weeks approx. 87% of the total toxaphene was degraded reaching 98% by week 39. The majority of the conversion took place in the anaerobic reactor. The concentrations of toxaphene isomers with more chlorine substituents decreased more rapidly than for isomers with less chlorine substituents.