Integrated assessment for aerobic biodegradability of organic substances

In this paper, the amount of oxygen consumption, end products and activities of microorganisms are considered as the three factors which affect the biodegradability of organic substances in water. Two integrated assessment methods for biodegradability of organic substances, fuzzy clustering integrated assessment and weighted integrated assessment, have been developed. Simultaneously, the detail steps for assessing a new organic substance biodegradability with these two integrated assessment methods are proposed.     

The biodegradability and microbial toxicity testing of lubricants--some recommendations

In recent years there has been a growing demand for information on the biodegradability (fate) and microbial toxicity (effects) of lubricants. This has been driven by the need to comply with environmental legislation and to meet the requirements of ecolabelling schemes, standards and customer specifications for 'environmentally acceptable' lubricants. This paper describes suitable approaches for generating this information under a variety of environmental conditions (e.g. aerobic, anaerobic, freshwater, marine), gives examples of the results obtained and discusses their interpretation. Recommendations on the use of each test are made.     

Chlorothalonil binding to aquatic humic substances assessed from gas purge studies

Abstract

Fate of the fungicide chlorothalonil (TCIN) binding to dissolved organic acid fractions was quantified using gas‐purge desorption studies. Binding studies were conducted to measure the dissolved organic carbon partition constant (K_DOC) with aquatic fulvic and humic acid fractions purified from cranberry bog water. Desorption studies at DOC concentrations up to 50 mg L^‐1 resulted in mean log K_DOC values of 4.63 (s.d.=0.5, n=8) and 4.81 (s.d.=0.7, n=7) for fulvic and humic acids, respectively. These values deviated from reported K_OC (organic carbon) values by 0.5 to 1.5 orders of magnitude. The relationship between K_OC and K_DOC did not conform to accepted ratios of 10: 1 to 3: 1, although these studies were conducted with the strong hydrophobic fraction of DOC. Binding was rapid suggesting hydrophobic partitioning or weak Van Der Waals forces as binding mechanisms. The strong binding potential for TCIN to aquatic humic substances corresponds to increased solubility in the aqueous system. Sorption to DOC suggests a possible transport mechanism which may result in elevated concentrations of TCIN in cranberry bog systems.     

Substitutes for phosphate containing washing products: Their toxicity and biodegradability in the aquatic environment

The toxicity of nitrolotriacetic acid (NTA), citrex-S-5, sodium alluminium silicate (NAS), carboxymethyloxysuccinate (CMOS), linear alkylbenzene sulfonate (LAS) and soap was examined using bacteria ($\text{Pseudomonas}$$\text{fluorescens}$), algae ($\text{Chlorella}$$\text{vulgaris}$ and $\text{Microcystis}$$\text{aeruginosa}$), crustaceans ($\text{Daphnia}$$\text{magna}$), insects ($\text{Aedes}$$\text{aegypti}$), fishes ($\text{Poecilia}$$\text{reticulata}$ and $\text{Oryzias}$$\text{latipes}$) and amphibians ($\text{Xenopus}$$\text{laevis}$). The biodegradability of NTA, citrex-S-5, CMOS and LAS was studied in the OECD-test.The acute toxicity of the compounds differed largely with the organisms tested (up to a factor 1,000). Based on the results of the short-term toxicity tests (with all test organisms) and the long-term toxicity tests (with $\text{Daphnia}$$\text{magna}$ and in case of LAS also with $\text{Poecilia}$$\text{reticulata}$) the following no-observed-effect concentrations (NOEC) could be derived: LAS 3.2 mg/1; NAS and soap 10 mg/1; CMOS 32 mg/1; NTA 100 mg/1 and citrex-S-5 320 mg/1. However, testing different samples of one test compound may result in marked differences in toxicity (e.g. NAS: a factor 32).All compounds tested showed to be biodegradable as the percentage DOC decreased more than 80% within four weeks. CMOS biodegraded quickly, whereas citrex-S-5 and LAS showed a somewhat slower rate of degradation. In contrast to the other compounds NTA required an adaptation period of 1 week.     

Evaluation of TCDD biodegradability under different redox conditions

Polychlorinated dibenzo-p-dioxins have been generated as unwanted by-products in many industrial processes. Although their widespread distribution in different environmental compartments has been recognized, little is known about their fate in the ultimate environment sinks. The highly stable dioxin isomer 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been called the most toxic compound known to man. In this laboratory microcosm study, TCDD bioavailability was evaluated under five reduction/oxidation (redox) conditions including aerobic biodegradation, aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Activated sludge and aquifer sediments from a TCDD and a pentachlorophenol (PCP) contaminated site were used as the inocula. Acetate, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in cometabolism and reductive dechlorination microcosms. After a 90-day incubation period, microcosms constructed under reductive dechlorination conditions were the only treatment showing promising remediation results. The highest TCDD degradation rate [up to 86% of TCDD removal (with an initial concentration of 96 microg/kg of soil)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cakes as the primary substrates. Except for reductive dechlorination microcosms, no significant TCDD removal was observed in the microcosms prepared under other conditions. Thus, application of an effective primary substrate to enhance the reductive dechlorination process is a feasible method for TCDD bioremediation. Bioremediation expense can be significantly reduced by the supplement of some less expensive alternative substrates (e.g., sludge cakes, cane molasses). Results would be useful in designing a scale-up in situ or on-site bioremediation system such as bioslurry reactor for field application.     

Testing toxicity of volatile substances with algae

A modification of the AAPBT (USEPA) for toxicity batch tests on volatile substances is described. The procedure permits maintenance of a constant concentration of toxicant in the culture and calculation of the concentration in the culture medium at the equilibrium, on the basis of physical characteristics of the chemical. The results of the application of the method on five chlorobenzenes are reported and compared with literature data.     

膜分离腐殖质前后晚期渗滤液可生化性的变化

晚期渗滤液由于含有大量难降解有机物腐殖质,可生化性差,较难处理.采用特定分子量的超滤膜对晚期渗滤液中的腐殖质进行有效的分离,研究了膜分离腐殖质前后渗滤液的可生化性的变化:渗滤液中腐殖质类物质去除率为90.7%,BOD5/COD值提高了6倍,可生物降解的有机物在总有机物中所占比率提高了约4倍.结果表明,分离腐殖质可提高渗滤液的可生化性.     

Effect of the alkyl chain length on the anaerobic biodegradability and toxicity of quaternary ammonium based surfactants

The anaerobic biodegradability and toxicity to methanogenic gas production of different alkyl chain length homologs of quaternary ammonium based surfactants were examinated. Two series of these cationic surfactants were selected: alkyl trimethyl ammonium and alkyl benzyl dimethyl ammonium compounds. A simple anaerobic gas production test containing municipal digester solids as a source of anaerobic bacteria was used. Under the applied methanogenic conditions, the cationic surfactants tested showed a very poor primary biodegradation and no evidence of any extent of ultimate biodegradation was observed. The toxicity of quaternary ammonium based surfactants to methanogenic gas production decreased with increasing the alkyl chain length.     

Electro-Fenton pretreatment for the improvement of tylosin biodegradability

The feasibility of an electro-Fenton process to treat tylosin (TYL), a non-biodegradable antibiotic, was examined in a discontinuous electrochemical cell with divided cathodic and anodic compartments. Only 15 min electrolysis was needed for total tylosin degradation using a carbon felt cathode and a platinum anode; while 6 h electrolysis was needed to achieve high oxidation and mineralization yields, 96 and 88 % respectively. Biodegradability improvement was shown since BOD₅/COD increased from 0 initially to 0.6 after 6 h electrolysis (for 100 mg L^?1 initial TYL). With the aim of combining electro-Fenton with a biological treatment, an oxidation time in the range 2 to 4 h has been however considered. Results of AOS (average oxidation state) and COD/TOC suggested that the pretreatment could be stopped after 2 h rather than 4 h; while in the same time, the increase of biodegradability between 2 and 4 h suggested that this latter duration seemed more appropriate. In order to conclude, biological cultures have been therefore carried out for various electrolysis times. TYL solutions electrolyzed during 2 and 4 h were then treated with activated sludge during 25 days, showing 57 and 67 % total organic carbon (TOC) removal, respectively, namely 77 and 88 % overall TOC removal if both processes were considered. Activated sludge cultures appeared, therefore, in agreement with the assessment made from the analysis of physico-chemical parameters (AOS and COD/TOC), since the gain in terms of mineralization expected from increasing electrolysis duration appeared too low to balance the additional energy consumption.     

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.     

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.     

Anaerobic biodegradability and methanogenic toxicity of key constituents in copper chemical mechanical planarization effluents of the semiconductor industry

Copper chemical mechanical planarization (CMP) effluents can account for 30-40% of the water discharge in semiconductor manufacturing. CMP effluents contain high concentrations of soluble copper and a complex mixture of organic constituents. The aim of this study is to perform a preliminary assessment of the treatability of CMP effluents in anaerobic sulfidogenic bioreactors inoculated with anaerobic granular sludge by testing individual compounds expected in the CMP effluents. Of all the compounds tested (copper (II), benzotriazoles, polyethylene glycol (M(n) 300), polyethylene glycol (M(n) 860) monooleate, perfluoro-1-octane sulfonate, citric acid, oxalic acid and isopropanol) only copper was found to be inhibitory to methanogenic activity at the concentrations tested. Most of the organic compounds tested were biodegradable with the exception of perfluoro-1-octane sulfonate and benzotriazoles under sulfate reducing conditions and with the exception of the same compounds as well as Triton X-100 under methanogenic conditions. The susceptibility of key components in CMP effluents to anaerobic biodegradation combined with their low microbial inhibition suggest that CMP effluents should be amenable to biological treatment in sulfate reducing bioreactors.     

Evaluation of lipid peroxidation as a toxicity bioassay for plants exposed to copper

Agricultural soils may contain toxic levels of copper (Cu) due to sewage sludge spreading or industrial pollution but chemical analyses may not be representative of Cu bioavailability, defined as the soil Cu fraction that plants can actually absorb (i.e. Cu fraction which is not strongly adsorbed to soil components). Lipid peroxidation caused by Cu in plants was investigated as a relevant bioassay of toxicity. Seven-day-old rapeseed plantlets were grown on Cu-supplemented medium in controlled conditions. Lipid-peroxidation was assessed by measuring: (1) the 2-thiobarbituric acid (TBA)-reactive substances; (2) the hydroperoxy acids by HPLC analysis; and (3) the alkane outputs by gas chromatography. We first verified the correlation between the results obtained by each method and then discussed their advantages and disadvantages within the context of a bioassay, showing that the volatile alkane output measurement is the most precise and easy to perform method for this purpose.     

Evaluation of time-to-effects as a basis for quantifying the toxicity of contaminated sediments

Due to uncertainties as to appropriate procedures and dilution materials, most sediment tests are conducted only with undiluted, whole samples. Hence, it is not possible to use conventional concentration-response approaches to quantify toxicity of samples that elicit a 100% effect (e.g., mortality) at a preset test interval (typically 10 d). An alternative approach to quantifying the relative toxicity of test sediments is to determine time-to-effects. The objective of this study was to assess the utility of a time-to-effects approach for quantifying toxicity of freshwater sediments to the invertebrates Hyalella azteca and Chironomus tentans. Survival of both species and growth of C. tentans was determined using five sediments (four test samples and a control sediment) by destructively sampling replicate test chambers over the course of a "standard" 10-d assay. Studies with the control sediment and a non-toxic test sample indicated excellent recovery of test animals, even early in the test (e.g., <24 h) when individuals of both species are relatively small. Reasonable, typically monotonic, time-to-death relationships were observed for both H. azteca and C. tentans exposed to three comparatively toxic test sediments, all of which caused significant mortality by 10 d. Use of the time-to-effects approach allowed expression of toxicity of the three samples relative to one another, as well as documentation of decreases in toxicity of one of the sediments with increased storage time. These studies demonstrate the feasibility of use of time-to-effects as a basis for quantifying the relative toxicity of contaminated sediments.     

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.     

Evaluation of post-Katrina flooded soils for contaminants and toxicity to the soil invertebrates Eisenia fetida and Caenorhabditis elegans

This research evaluated soil samples from a New Orleans neighborhood in the Chalmette, Saint Bernard Parish, that had been inundated by flooding associated with Hurricane Katrina. The goal was to determine if ecological risks persisted from flood waters that had come in contact with hazardous surface chemicals before inundating this low-lying neighborhood for a prolonged period. Research objectives were to establish the presence or absence of volatile organic and heavy metal contaminants, and then asses the toxicity of this soil to Eisenia fetida in a soil exposure assay and Caenorhabditis elegans in a simulated porewater exposure assay. Soil analysis revealed detectable levels of metals and organics in the surface soil at each location. No contaminant was detected in concentrations above human health screening values. Chromium and mercury were detected at levels in excess of typical ecological risk values. Soil extracts revealed concentrations of nitrate, sulfate, and chloride above those from an unflooded background sample. Toxicity testing resulted in no acute effects to either test species, but did show bioaccumulation of arsenic, cadmium, and lead in E. fetida exposed to several samples. The combination of mercury and sulfate provide the potential for mercury methylation should flooding and prolonged inundation occur again.     

The algal toxicity of silver engineered nanoparticles and detoxification by exopolymeric substances

In this study, we report that silver ions (Ag⁺) from the oxidative dissolution of silver engineered nanoparticles (Ag-ENs) determined the EN toxicity to the marine diatom Thalassiosira weissflogii. Most of the Ag-ENs formed non-toxic aggregates (>0.22 μm) in seawater. When the free Ag⁺ concentration ([Ag⁺]_F) was greatly reduced by diafiltration or thiol complexation, no toxicity was observed, even though the Ag-ENs were better dispersed in the presence of thiols with up to 1.08 × 10⁻⁵ M Ag-ENs found in the <0.22 μm fraction, which are orders of magnitude higher than predicted for the natural aquatic environment. The secretion of polysaccharide-rich algal exopolymeric substances (EPS) significantly increased at increasing [Ag⁺]_F. Both dissolved and particulate polysaccharide concentrations were higher for nutrient-limited cells, coinciding with their higher Ag⁺ tolerance, suggesting that EPS may be involved in Ag⁺ detoxification.     

A simple screening test for studying the biodegradability of insoluble polymers

The head-space test based on CO₂ measurement was improved as a test for determining of the biodegradability of solid polymers, such as biodegradable plastics. The test can be performed either as closed or aerated cultures depending on the size of the sample and its oxygen demand. The distribution of CO₂ between the gas and liquid phases was also determined during the cultivations. The amount of microbial carbon was determined indirectly by determining the carbon/protein ratio and then using the intracellular protein as an indirect measure of the biomass. The amount of biomass was found to be so low that its determination did not significantly effect the final biodegradation result.