The need for applying stability tests in biodegradability assessments

Out of fourteen chemicals tested, two - hexamethylenetetramine and sodium benzene sulphinate - were degraded in screening tests (>70% DOC removal, >60% ThOD exerted) but not in activated sludge simulation tests (<25% DOC removal). It is suggested from data in the literature that these essentially non-biodegradable chemicals undergo hydrolysis or autoxidation in the 28-day screening tests to form biodegradable products, which are not produced in sufficient quantity in the 3-hour simulation test. The need is stressed for taking account of the stability of chemicals in water when assessing biodegradability in the environment.     

Ultimate biodegradation and elimination of antibiotics in inherent tests

The biodegradation and elimination of antibiotics in municipal wastewater treatment plants is of particular concern because sewage is the main exposure route for antibiotics used in human medicine. The inherent biodegradability of 17 antibiotics was determined in a combined test design based on the Zahn-Wellens test (OECD 302 B, 1992) and the CO2-evolution test (OECD 301 B, 1992). CO2 Evolution test (Modified Sturm test). OECD Guideline for the Testing of Chemicals, Paris). Only benzylpenicillin sodium salt (Penicillin G) proved to be ultimately biodegradable, reaching ThCO2 degradation extents of 78-87%. Among the others, only amoxicillin, imipenem and nystatin showed certain ultimate biodegradation in few of the parallel flasks and can be regarded as partially biodegradable with formation of stable metabolites. The DOC-elimination of tetracycline-HCl showed a typical degradation curve starting with 18% and reaching the plateau phase at 80% after 21 days. Nevertheless, the CO2-evolution measured in parallel did not support the data, indicating that the time needed for reaching the adsorption equilibrium was underestimated. Several other antibiotics showed considerable DOC-elimination in the inherent test while only minor incidences of ultimate biodegradation were observed. The combination of CO2-evolution and DOC-elimination is a suitable instrument for assessing the behaviour of chemicals within one test. It enables one to assess both inherent ultimate biodegradability and DOC-elimination by sorption. The applicability of the test is limited to substances with a moderate toxicity.     

Evaluation of laboratory-made sludge for an anaerobic biodegradability test and its use for assessment of 13 chemicals

Laboratory-made sludge for a biogas based anaerobic biodegradability test was prepared as an alternative for digested sludge from wastewater treatment plants (WWTPs). Biodegradation activities and background gas productions of digested sludge from various WWTPs were found to vary significantly depending on the source, which adversely affected test reliability. Subsequently, test conditions such as sludge concentration and sludge washing were examined with the laboratory-made sludge and a sludge concentration of 1.0 g-SS/L without washing was determined to be most suitable. Under these conditions, biodegradability tests were conducted for 13 select chemicals and their relative toxicities to methanogenic bacteria were evaluated. The results of biodegradability tests showed that chemicals with -OH and -CH2OH radicals were readily biodegraded and those with -Cl, -NO2, -NH2, -SO3H and -CH3 had inhibited degradation responses m-nitriphenol and 2,4,6-trichlorophenol were highly toxic to methanogenic bacteria, with m-nitrophenol completely inhibiting methane fermentation as low as 20 mg/L.     

A method for measuring the anoxic biodegradability under denitrifying conditions

A test for assessing the anoxic biodegradability of organic compounds under denitrifying conditions is proposed. The method is based on the recovery and quantification of the CO2 produced, which is evidence of complete biodegradation of the test compound (added as the sole carbon source). The tests were carried out in a mineral medium, with nitrate as electron acceptor. Whole lake sediments, sediment extracts and a commercial inoculum were assayed as a possible inoculum source by means of glucose biodegradability tests. It was found that the sediment extracts constitute a suitable and environmentally-relevant inoculum source, since they add non-significant amounts of carbon to the tests. Two xenobiotic compounds, namely, aniline and phenol, were tested in the aforementioned conditions as well as in a standard aerobic biodegradability test. Both aniline and phenol attained a biodegradation level higher than 60% in a short time period (<28 days) and thus can be considered as readily biodegradable in denitrifying environments. Nevertheless, the kinetics obtained in the anoxic test were slower than in aerobic conditions, and even suggested the accumulation of intermediate metabolites in the case of phenol. The results of this study indicate that the fate of xenobiotic compounds under anoxic conditions differs from that observed in an oxic environment, and therefore it should be considered by standard biodegradability testing procedures.     

Analytical approaches for determining human exposure to pesticides

Abstract

The presence of pesticides, both persistent and biodegradable, in the environment is a problem which is both significant and potentially dangerous to humans. An index of biodegradability is presented which is based on the correlation between environmental stability and fat solubility. Halogenated pesticides are, therefore, both more fat soluable and more resistant to biodegradation, while methylated pesticides are more water soluable and, therefore, more biodegradable. Three methods for detecting low‐levels of halogenated pesticides are presented: the Macro, the Micro “Florisil,”; and the Micro “Silica.”; A method is also presented to detect these chemicals in blood. Two methods for the detection of nonpersistent, organophosphorus and carbamate insecticides, Cholinesterase inhibition and urinary metabolites, are described. Finally, methods of monitoring human exposure through the detection of phenols, phenoxy acids, alkyl phophates, and anilines are presented.     

Biodegradability and ecotoxicity of amine oxide based surfactants

The aerobic and anaerobic biodegradability as well as the aquatic toxicity of two fatty amine oxides and one fatty amido amine oxide were investigated. Aerobic biodegradation was evaluated using the CO(2) headspace test (ISO 14593) and biodegradation under anaerobic conditions was assessed employing a standardised batch test. The three amine oxide based surfactants tested were readily biodegradable under aerobic conditions but only the alkyl amido amine oxide was found to be easily biodegradable under anaerobic conditions. Toxicity to Photobacterium phosphoreum and Daphnia magna was evaluated. Bacteria (EC(50) from 0.11 to 11 mg l(-1)) proved to be more sensitive to the toxic effects of the amine oxide based surfactants than crustacea (IC(50) from 6.8 to 45 mg l(-1)). The fatty amido amine oxide showed the lowest aquatic toxicity.     

Assessment of degradation of 18 antibiotics in the Closed Bottle Test

Large quantities of antibiotics are used in health care. After administration, they are discharged into the effluent and reach sewage treatment plants (STPs); if they are not degraded, they will eventually enter the environment. Antibiotics can affect bacteria in the environment and thus disturb natural elemental cycles. For this reason, it is necessary to take a closer look at the fate and effects of these substances in the environment. The biodegradability of 18 clinically important antibiotics and their effects on environmental bacteria was studied using the Closed Bottle Test (CBT) (OECD 301 D 1992). In addition, a toxicity control was performed in the CBT and the colony forming units (CFUs) were monitored. Disappearance of some of the 18 antibiotics was monitored by HPLC (high performance liquid chromatography) analysis. The antibiotics were used in two concentrations: (a) according to OECD 301 D in the mg/l-range and (b) on the basis of calculated concentrations in the influent of STPs in the microg/l-range. None of the 18 antibiotics were readily biodegradable. The HPLC analysis showed that some substances were partially or even completely disappeared by a non-biotic mechanism. In the case of some antibiotics, partial biological removal took place in test vessels containing readily biodegradable sodium acetate and the test compound. However, in the toxicity control, toxicity had not been eliminated.     

Effects of livestock wastewater variety and disinfectants on the performance of constructed wetlands in organic matters and nitrogen removal

Background, aim and scope  

Treatment performance of constructed wetlands (CWs) is largely dependent on the characteristics of the wastewater. Although livestock wastewater is readily biodegradable in general, its variety in biodegradability can still be significant in practice. In addition, it is a common practice to periodically use disinfectants in livestock activities for health concerns. Obviously, the residual of the disinfectants in livestock wastewater may have serious inhibitory effect on the microbial activities during wastewater treatment. Thus, the main objective of this study was to examine the variety of livestock wastewater in biodegradability and its effect on the performance of a pilot scale tidal flow CWs (TFCWs) in organic matter and nitrogen removal. Furthermore, investigation of the potential inhibition of the chosen disinfectants on organic matter biodegradation and nitrification was another aim of this study.     

Biodegradation and toxicity of wastewater from industry producing mineral fibres for thermal insulation

The water chemistry, toxicity, and biodegradation of wastewater from an industry producing mineral fibres for thermal insulation were studied. Values for COD, BOD5, suspended solids, and phenol exceeded permissible values for the wastewater discharged into a nearby river and acute toxicity was also detected. Consequently, the effluent should be treated in a municipal wastewater treatment plant so its ready biodegradability was investigated. We found that the wastewater was readily biodegradable, therefore we assume it can be treated in the wastewater treatment plant as the ratio of the wastewater flow rate and the minimal total inflow into the sewage treatment plant would be one to at least 30.     

Measuring the biodegradability of nonylphenol ether carboxylates, octylphenol ether carboxylates, and nonylphenol

We examined the biodegradability of several metabolites of C8- and C9-alkylphenol ethoxylates, including nonylphenoxyacetic acid (NPEC1), nonylphenoxyethoxyacetic acid (NPEC2), octylphenoxyacetic acid (OPEC1), octylphenoxyethoxyacetic acid (OPEC2), and nonylphenol (NP). Using OECD method 301B (modified Sturm method), OPEC1 and OPEC2 are readily biodegradable: both compounds exceeded 60% of theoretical CO2 formation (ThCO2) by day 28, and required less than 10 days to go from 10% to 60% ThCO2. Also using method 301B, NPEC1 and NPEC2 exceeded 60% ThCO2 at day 28, but did not meet the 10 day window. Using OECD method 301F, the manometric respirometry method that measures oxygen consumption, approximately 62% of NP was biodegraded in 28 days, but required more than 10 days to go from 10% to 60% biodegradation. While the validity of the "10-day window" is currently being debated within OECD, the data show that the common metabolites of C8- and C9-APEs are rapidly degraded in the test systems used, which strongly suggests that they would not accumulate or persist in the environment.     

Application of the headspace CO2 method (ISO 14 593) to the assessment of the ultimate biodegradability of surfactants: results of a calibration exercise

In the recent review of the control of marketing surfactants used in detergents, the EU decided to increase the severity of the testing procedure by using the criterion of ultimate biodegradability (mineralization) rather than primary biodegradation (removal of the parent molecule) to ensure that possible harmful organic metabolites do not reach the environment. The relatively new ISO headspace CO2 test, considered to be an improvement on the OECD 301B (Sturm CO2) test was chosen. The method was subjected to a ring test by 11 laboratories using one of each of four classes of surfactants plus a poorly degradable reference surfactant; all laboratories satisfactorily applied the method. The necessary addition of silica gel to the medium containing the cationic surfactant, known as a class to be more inhibitory than other classes, was confirmed as a technique for avoiding inhibition of the inoculum. The biodegradability of the surfactants was in general agreement with results reported in the literature and the often reported variable values of % inorganic carbon (IC) produced of the theoretical was found. The anionic and cationic surfactants were readily biodegradable (%IC > 60), the non-ionic surfactant was well below the pass value, while the amphoteric was borderline. The IC production by the blank controls, one of the validity criteria, was about 0.3 mg C/100 ml test medium, equivalent to 3 mg C/l, as recommended in the ISO text. Mild conditions of pre-exposure of the inoculum to the test surfactant did not produce consistent worthwhile effects on either the percentage biodegradation or on its variability.     

Biodegradation of chemicals in a standardized test and in environmental conditions

The estimation of biodegradation rates is an important source of uncertainty in chemical risk assessment. The existing OECD tests for ready biodegradability have been developed to devise screening methods to determine whether a chemical is potentially easily biodegradable, rather than to predict the actual rate, of biodegradation in the environment. However, risk assessment needs degradation rates. In practice these rates are often estimated (default values) from ready biodegradability tests. These tests have many compromising arbitrary features compared to the situation in the real environment. One important difference is the concentration of the chemical. In wastewater treatment or in the environment many chemicals are present at ng l(-1) to microg l(-1) levels whereas in the tests the concentrations exceed 10-400 mg carbon per litre. These different concentrations of the chemical will lead to different growth kinetics and hence different biodegradation rates. At high concentrations the chemical, if it is degradable, can serve as a primary substrate and competent microorganisms will grow exponentially, resulting in a sigmoid biodegradation curve. At low environmental concentrations the chemical does not serve as a primary substrate, and therefore does not support significant growth of the degraders, and the substrate has a linear biodegradation rate. In this study the biodegradation rates of two reference chemicals, aniline and 4-chloroaniline, were compared in a standard method and in more realistic conditions at low concentrations, using 14C-labelled substances and different sources of inocula. Biomass evolution during the tests was monitored by adenosine triphosphate measurement and also on the basis of the residual 14C-activity in the particulate matter. The results partly support the thesis that low concentrations lead to different biodegradation kinetics compared to the concentrations used in the standard tests. Furthermore the biodegradation rates of the chemicals studied, particularly of 4-chloroaniline, in Finnish natural waters appeared to be lower than those reported in some other countries.     

Properties of aminotris (methylenephosphonate) affecting its environmental fate: Degradability,sludge adsorption,mobility in soils,and bioconcentration

In spite of its low aerobic and anaerobic biodegradability ATMP was shown to be quantitatively decomposed in a number of natural and synthetic waters. The primary products formed are iminodi (methylenephosphonate) (IDMP) and the biodegradable hydroxymethylenephosphonate (HMP). Furthermore, IDMP is abiotically degraded yielding HMP and aminomethylenephosphonate (AMP). The latter was shown to be biodegradable under certain environmental conditions. A degradation mechanism similar to that of ATMP was indicated for ethylenediaminetetra (methylenephosphonate) (EDTMP). ATMP was characterized by adsorption studies as having moderate to low mobility in soils. A very low bioconcentration potential of ATMP was demonstrated in a dynamic bioaccumulation fish test.     

偶氮染料结构与其生物降解性关系研究进展

本文阐述了偶氮染料结构－生物降解性定性关系，生物降解机制，并对偶氮染料结构－生物降解性定量关系的有关参数进行了论述。     

活性污泥1号模型废水特性的测定研究

废水的水质特性是活性污泥数学模型研究和应用的重要方面。采用呼吸计量法及常规化学分析法对污水处理厂的废水特性进行了测定,通过研究发现,污水处理厂的曝气沉砂池出水中SS占总COD的比例平均为10．49％;Xs占总COD的比例平均为14．24％;S1占总COD的比例平均为5．52％。初沉池出水中Ss占总COD的平均比例为9．62％;Xs占总COD的比例平均为16．97％;S1占总COD的比例平均为11．38％。     

Laboratory simulation of biodegradation of chemicals in surface waters: closed bottle and respirometric test

Microbial degradation is the most dominant elimination mechanism of organics from the environment. For evaluation of biodegradability of pure chemicals many standardized tests are available, but no standardized procedure for assessment of biodegradability of chemicals in surface water is agreed upon. Rates of in-situ biodegradation are usually estimated in laboratory simulation where environmental factors are reproduced to some extent. The aim of our study was to compare standardised ready biodegradability assessment, test (Closed bottle test) and its modifications employing the basic agreements on test conditions to simulate biodegradation in surface water. Standard test was modified using various natural river waters to simulate the natural environment in a simplified way. The impact of different types and amounts of nutrients and microorganisms on biodegradation was confirmed. The conditions in the recipient should be examined to extrapolate the results from ready biodegradability tests to real surface water.     

Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater

This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.     

Advanced oxidation of a pulp mill bleaching wastewater.

The degradation, by several advanced oxidation reactions, of a pulp mill ECF bleaching effluent, was studied. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD5/COD, was low (0.3). When the effluent was submitted to ozonation and to five different advanced oxidation systems (O3/UV, O3/UV/ZnO, O3/UV/TiO2, O2/UV/ZnO, O2/UV/TiO2), the biodegradability increase significantly. After five minutes of reaction, the O3/UV system appears as the most efficient in to transform the organic matter to more biodegradable forms. A similar effect was observed when the effluent was submitted to an activated sludge treatment. The COD, TOC and toxicity reduction correlated well with the biodegradability enhancement after AOPs treatments.     

Biodegradation potential of ofloxacin and its resulting transformation products during photolytic and photocatalytic treatment

The release of pharmaceuticals in the environment, as parent compounds, metabolites and transformation products, and the consequent risks posed to living organisms due to the unintended exposure of the latter to these chemicals are nowadays of increasing scientific concern. The development of advanced oxidation processes able to degrade these substances is in the core of the current research objectives, the main target being the removal of these compounds from wastewaters. Often the focus is on the removal of the parent compound only. However, these processes can form transformation products. Knowledge on the risk related to such transformation products is scarce. Among others, knowledge on their toxic effects and their biodegradability is of importance not only when they are present in the environment but also for the assessment of the advanced oxidation processes’ efficiency applied for their degradation. Photolytic (UV irradiation) and photocatalytic treatment (UV irradiation in the presence of TiO₂) of the fluoroquinolone ofloxacin were applied, and the biodegradability of the formed products was investigated using the Closed Bottle test (OECD 301 D). Various transformation products, formed both during the photo(cata)lytic treatment and the Closed Bottle test, were identified using chromatographic analysis with an ultra high-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) system. The transformation products formed during the phototreatments were found to be non-readily biodegradable as the biodegradation percentages were close to zero. The persistence of the various photo(cata)lytic transformation products during the Closed Bottle test may be attributed to the fluorine present in all the transformation products formed. The transformation products identified suggest that two transformation routes were present: decarboxylation and opening of the piperazinyl ring. Interestingly, it was observed that in the presence of a readily biodegradable carbon source (sodium acetate), the biodegradation percentage increased drastically for some of the photolytically treated samples. This was not the case for the photocatalytically treated samples, in which also mineralization of the parent compound was achieved faster. Further research is needed, however, in order to increase the understanding of the conditions that may lead to less potent and persistent substances during the application of such engineered or natural processes.