Changes in toxicity and genotoxicity of industrial sewage sludge samples containing nitro- and amino-aromatic compounds following treatment in bioreactors with different oxygen regimes

Goals, Scope and Background

From 2005, deposition of organic waste will be banned in Sweden. Likewise, in Germany and Austria, similar bans are being planned, and further countries will probably follow. Thus, there is a need to develop new methods and to refine established techniques for sludge management in the whole of the European Union. For this end, there is also an urgent need for appropriate ecotoxicological approaches to elucidate and assess the hazard potential of sewage sludge. Therefore, the present study was designed to assess the capacity of various established sludge treatment methods using different oxygen regimes to degrade recalcitrant nitro-substituted organic compounds and reduce their toxicity. Sewage sludge samples from a wastewater treatment plant in Sweden (Cambrex Karlskoga AB, industrial area Björkborn) receiving wastewater from industries manufacturing pharmaceutical substances, chemical intermediates and explosives were processed with different sludge treatment methods. Among other treatment methods, bioreactors (for anaerobic and aerobic sludge treatment) were used. In the present investigation, a battery ofin vitro bioassays was employed to compare the cytotoxic and genotoxic potentials of different fractions of sludge samples in order to elucidate whether the treatments were suitable to reduce the toxicity of the sludge.

Methods

In order to investigate the cytotoxicity of the extracts of treated and untreated sludge samples, the acute cytotoxicity test with the permanent cell line RTL-W1 was used. Genotoxicity was tested by means of the comet assay (single cell gel electro-phoresis) with RTL-W1cells, and mutagenicity was assessed with the Ames test using the Salmonella typhimurium strains TA98, TA98NR and TA100. Sludge toxicity was tested in different fractions of organic extracts produced by acetone and hexane extractions. The subsequent clean-up procedure (silica gel chro-matography and elution with hexane and dichloromethane) resulted in two fractions, a lipophilic hexane-fraction and a semi-lipophilic dichloromethane-fraction. For the genotoxicity and mutagenicity tests, these fractions were reunited at equal ratios.

Results and Discussion

The acute cytotoxicity test with RTL-Wl cells revealed a high cytotoxic potential for the semi-li-pophilic DM-fractions of all sludge samples with NR₅₀ values (= effective concentration for 50% cell death in the neutral red test) from 8.9 up to 20 mg sludge d.w./ml medium. A low cytotoxic potential for the hexane fractions of the untreated sludge samples (NR₅₀ 400 to < 400 mg sludge d.w./ml medium) was observed, whereas the hexane fractions of the treated sludge samples showed elevated cytotoxicity increasing further with treatment in the bioreactors. The comet assay indicated that three out of eight of the reunited fractions had a significant genotoxic potential. Whereas the genotoxic potential of one sample treated anaerobically was very high with an induction factor of 11.6, a similar sample (taken from the same anaerobic reactor four months later) and one untreated sample showed lower potentials. The samples treated in another anaerobic bioreactor as well as the samples treated aerobically showed no genotoxic potential. Results indicate that aerobic treatment was basically adequate for reducing the genotoxicity of the sludge, whereas anaerobic treatment was only partly useful for reduction of genotoxicity. The Ames test revealed a very high mutagenic potential for the reunited fractions of the untreated sludge samples with strain TA98 (maximum induction factors (IF_max up to 45) and a relatively high potential for one of the samples treated aerobically (S2, IF_max = 18 (TA98, S9-)), thus documenting the suitability of both anaerobic and aerobic treatments to reduce the mutagenicity of the samples, however, with the aerobic treatment being less effective. Conclusions. Overall, none of the microbiological treatments for wastewater sludge in bioreactors was found to be ideal for general toxicity reduction of the sludge samples. Whereas cytotoxicity of the sludge increased or levelled off in most cases following either treatment, genotoxicity both increased or decreased after anaerobic treatment, depending on the specific sample. However, mutagenicity could generally be reduced by anaerobic treatment and, to a lesser degree, by aerobic treatment. Recommendationsand Perspectives. The complex modification of the diverse damage potentials of sludge sample extracts by use of anin vitro biotest battery following treatment for toxicity reduction in bioreactors showed that considerations of different toxicological endpoints is essential for an adequate hazard assessment. Whereas in the case of cytotoxicity reduction, the reactors proved ineffective, mutagenicity could be reduced significantly at least in some cases in this case study.

     

A level change in mutagenicity of Japanese tap water over the past 12 yr

A relative comparison study of mutagenicity in Japanese tap water was conducted for 1993 and 2005 surveys. It intended to assess the effects of advanced water treatment installations to water works, improvement of raw water quality and improvement of residual HOCl concentration controlling. Sampling points (taps) were the same in both surveys. The results of 245 samples obtained by the Ames Salmonella mutagenicity test (Ames test) were analyzed. The Ames tests were conducted by using Salmonella typhimurium TA98 and TA100 strains with and without exogenous activation (S9). With the exception of TA100-S9, the other conditions needed no discussion as a factor in the mutagenicity level change. The average mutagenicity in 1993 and 2005 under the conditions of TA100-S9 were 2600 and 1100 net revertant L⁻¹, respectively. This indicated that the mutagenicity level of Japanese tap water decreased during the 12-yr period. Particularly a remarkable decrease in mutagenicity was observed in the water works where the advanced water treatments were installed during the 12-yr period. The advanced water treatments were effective in decreasing the mutagenicity of tap water. Mutagenicity also decreased in the water works with conventional water treatments; the improvement of residual HOCl concentration controlling was also considered to be effective in decreasing the mutagenicity of tap water.     

Ex situ remediation of contaminated sediments using mineral additives: assessment of pollutant bioavailability with the Microtox solid phase test

The aim of this work is to assess the potential ecotoxicological effects of contaminated sediments treated with mineral additives. The Microtox solid phase test was used to evaluate the effect of mineral additives on the toxicity of sediment suspensions. Four Mediterranean port sediments were studied after dredging and bioremediation: Sample A from navy harbor, sample B from commercial port and samples C and D from pleasure ports. Sediment samples were stabilized with three mineral additives: hematite, zero-valent iron and zeolite. Results show that all studied mineral additives can act as stabilizer agent in highly contaminated sediments (A and C) by decreasing dissolved metal concentrations and sediment toxicity level. On the contrary, for the less contaminated samples (B and D) hematite and zeolite can provoke toxic effect towards Vibrio fischeri since additive particles can favor bacteria retention and decrease bioluminescence emission.     

The Mutagenic Activity of Particulate Organic Matter Collected with a Dilution Sampler at Coal-Fired Power Plants

The Deep Creek Lake Study of 1983 provided an opportunity to obtain emission samples from coal-fired power plants with a dilution sampler for mutagenicity testing. Stack and ambient samples of particulate matter were collected with a dilution sampler at three coal-fired power plants in West Virginia. Samples were sequentially extracted with cyclohexane (CX), dichloromethane (DCM) and acetone (ACE) and tested for mutagenicity in the Ames Salmonella/microsome assay using TA98 (-S9). For the stack samples, the CX, DCM and ACE fractions constituted 1.0, 0.7 and 98.1 percent of the total extractable organic material (EOM), respectively, compared to 28.5, 7.4 and 64.1 percent for the ambient samples. In contrast, the mutagenic activity of the organic fractions was concentrated in the CX and DCM fractions.

The cyclohexane- and dichloromethane-soluble fractions of the stack samples from all locations exhibited mutagenicity when tested in the plate incorporation assay. No significant response was observed with the acetone fraction. When tested with Kado's modification of the preincubation assay, the acetone-soluble fraction did exhibit mutagenic activity comparable to that of the other fractions when expressed in units of revertants per milligram of particular matter. Chemical analyses of one of the acetone-soluble fractions indicated that half of the mass was sulfuric acid while the remainder consisted of C, H and O. More than 30 peaks were detected in the high pressure liquid chromatogram of this fraction.

Although little mutagenic activity was detected in the polar ACE fraction of the diluted stack emissions samples with this single bioassay, in view of the large mass of this fraction, further investigation of the chemical composition and genotoxic activity of this fraction would be prudent.     

Bioassay-directed identification of toxic organic compounds in creosote-contaminated groundwater

Despite the fact that creosote mainly consists of polycyclic aromatic hydrocarbons (PAHs), more polar compounds like phenolics, benzenes and N-, S-, O-heterocyclics dominate the groundwater downstream from creosote-contaminated sites. In this study, bioassay-directed fractionation, combined with fullscan GC-MS, identified organic toxicants in creosote-contaminated groundwater. An organic extract of creosote-contaminated groundwater was fractionated on a polar silica column using high performance liquid chromatography (HPLC), and the toxicity of the fractions was measured by the Microtox-bioassay. PAHs, which comprise up to 85% of pure creosote, accounted for only about 13% of total toxicity in the creosote-contaminated groundwater, while methylated benzenes, phenolics and N-heterocyclics accounted for ca. 80% of the measured toxicity. The fraction containing alkylated quinolines was the most toxic single fraction, accounting for 26% of the total measured toxicity. The results imply that focus on PAHs may underestimate risks associated with creosote-contaminated groundwater, and that environmental risk assessment should focus to a higher degree on substituted PAHs and phenolics because they are more toxic than the unsubstituted ones. Additionally, benzenes and N-heterocyclics (e.g., alkylated quinolines) should be assessed.     

Health care industries: potential generators of genotoxic waste

Health care waste includes all the waste generated by health care establishments, research facilities, and laboratories. This constitutes a variety of chemical substances, such as pharmaceuticals, radionuclides, solvents, and disinfectants. Recently, scientists and environmentalists have discovered that wastewater produced by hospitals possesses toxic properties due to various toxic chemicals and pharmaceuticals capable of causing environmental impacts and even lethal effects to organisms in aquatic ecosystems. Many of these compounds resist normal wastewater treatment and end up in surface waters. Besides aquatic organisms, humans can be exposed through drinking water produced from contaminated surface water. Indeed, some of the substances found in wastewaters are genotoxic and are suspected to be potential contributors to certain cancers. The aim of this study was to evaluate the genotoxic and cytotoxic potential of wastewaters from two hospitals and three clinical diagnostic centers located in Jaipur (Rajasthan State), India using the prokaryotic Salmonella mutagenicity assay (Ames assay) and the eukaryotic Saccharomyces cerevisiae respiration inhibition assay. In the Ames assay, untreated wastewaters from both of the health care sectors resulted in significantly increased numbers of revertant colonies up to 1,000–4,050 as measured by the Salmonella typhimurium TA98 and TA100 strains (with and without metabolic activation) after exposure to undiluted samples, which indicated the highly genotoxic nature of these wastewaters. Furthermore, both hospital and diagnostic samples were found to be highly cytotoxic. Effective concentrations at which 20 % (EC₂₀) and 50 % (EC₅₀) inhibition of the respiration rate of the cells occurred ranged between ～0.00 and 0.52 % and between 0.005 and 41.30 % (calculated with the help of the MS excel software XLSTAT 2012.1.01; Addinsoft), respectively, as determined by the S. cerevisiae assay. The results indicated that hospital wastewaters contain genotoxic and cytotoxic components. In addition, diagnostic centers also represent small but significant sources of genotoxic and cytotoxic wastes.     

Characterization of Polycyclic Aromatic Hydrocarbons from the

Abstract

Diesel fuels governed by U.S. regulations are based on the index of the total aromatic contents. Three diesel fuels, containing various fractions of light cycle oil (LCO) and various sulfur, total polyaromatic, and total aromatic contents, were used in a heavy-duty diesel engine (HDDE) under transient cycle test to assess the feasibility of using current indices in managing the emissions of polycyclic aromatic hydrocarbons (PAHs) from HDDE. The mean sulfur content in LCO is 20.8 times as much as that of premium diesel fuel (PDF). The mean total polyaromatic content in LCO is 28.7 times as much as that of PDF, and the mean total aromatic content in LCO is 2.53 times as much as that of PDF. The total polyaromatic hydrocarbon emission factors in the exhaust from the diesel engine, as determined using PDF L3.5 (3.5% LCO and 96.5% PDF), L7.5 (7.5% LCO and 92.5% PDF), and L15 (15% LCO and 85% PDF) were 14.3, 25.8, 44, and 101 mg L^?1, respectively. The total benzo(a)pyrene equivalent (BaP_eq) emission factors in the exhaust from PDF, L3.5, L7.5, and L15 were 0.0402, 0.121, 0.219, and 0.548 mg L^?1, respectively. Results indicated that using L3.5 instead of PDF will result in an 80.4% and a 201% increase of emission for total PAHs and total BaP_eq, respectively. The relationships between the total polyaromatic hydrocarbon emission factor and the two emission control indices, including fuel polyaromatic content and fuel aromatic content, suggest that both indices could be used feasibly to regulate total PAH emissions. These results strongly suggest that LCO used in the traveling diesel vehicles significantly influences PAH emissions.     

Comparative use of bacterial, algal and protozoan tests to study toxicity of azo- and anthraquinone dyes

Toxicity of two azo dyes (Reactive Orange 16 (RO16); Congo Red (CR)) and two anthraquinone dyes (Remazol Brilliant Blue R (RBBR); Disperse Blue 3 (DB3)) were compared using bacterium Vibrio fischeri, microalga Selenastrum capricornutum and ciliate Tetrahymena pyriformis. The following respective endpoints were involved: acute toxicity measured as bacterial luminescence inhibition, algal growth inhibition, and the effects on the protozoa including viability, growth inhibition, grazing effect and morphometric effects. In addition, mutagenicity of the dyes was determined using Ames test with bacterium Salmonella typhimurium His(-). DB3 dye was the most toxic of all dyes in the bacterial, algal and protozoan tests. In contrast to other dyes, DB3 exhibited mutagenic effects after metabolic activation in vitro in all S. typhimurium strains used. Of the methods applied, the algal test was the most sensitive to evaluate toxicity of the dyes tested.     

Urban-Center CO Air Quality Projections

The distribution of mutagenic activity and nitroaromatic components of polycyclic organic matter (POM) in ambient air at industrial, urban, suburban, rural, and remote sites was studied using organic extracts from high volume aerosol samples. Direct-acting mutagens including 1-nitropyrene (1-NP), dinitropyrenes (DNP), and hydroxynitropyrenes (HNP) were measured by high performance liquid chromatography while the mutagenicity was determined in the Salmonella bioassay with strain TA-98. Benzo(a)pyrene (BaP), one of the possible precursors of nitroaromatic compounds in POM, was also measured. In comparing samples from a range of sites, TSP and the concentration of BaP per mass of particulate matter decreased, as expected, at greater distances from urban and industrial combustion sources. However, the concentrations of polar nitroaromatic POM compounds per mass of particles were higher at a remote site than in nonindustrial urban and suburban areas. The mutagenicity in particulate matter extracts from the remote area was predominantly (>90 percent) in the very polar fractions. There were also high atmospheric levels of nitroaromatic compounds and mutagenicity in heavily industrialized areas. These observations may reflect the influences of source emissions, atmospheric transformations of POM compounds, and ther atmospheric processes on the composition of ambient suspended particulate matter.     

Comparison of test procedures for sediment toxicity evaluation with Vibrio fischeri bacteria

The use of bacterial luminescence assays is particularly effective in the contaminated sediment evaluation. In the present study, a comparison was made of different baterial luminescence assays including acute toxicity of elutriates with Microtox® and LUMIStox®; chronic toxicity of elutriates with LUMIStox®; and, acute toxicity of solvent extracts with both the tests and the Solid Phase test with Microtox. The toxicity assay procedures were utilised for the Po River sediment toxicity evaluation, testing samples with different physical and chemical characteristics. The results evidentiated that each sediment test procedures provided indipendent and complementary ecotoxicological responces usefull for a sediment classification of the most polluted samples.     

The application of bioassays as indicators of petroleum-contaminated soil remediation

Bioremediation has proven successful in numerous applications to petroleum contaminated soils. However, questions remain as to the efficiency of bioremediation in lowering long-term soil toxicity. In the present study, the bioassays Spirotox, Microtox, Ostracodtoxkit F, umu-test with S-9 activation, and plant assays were applied, and compared to evaluate bioremediation processes in heavily petroleum contaminated soils. Six higher plant species (Secale cereale L., Lactuca sativa L., Zea mays L., Lepidium sativum L., Triticum vulgare L., Brassica oleracea L.) were used for bioassay tests based on seed germination and root elongation. The ecotoxicological analyses were made in DMSO/H2O and DCM/DMSO soil extracts. Soils were tested from two biopiles at the Czechowice oil refinery, Poland, that have been subjected to different bioremediation applications. In biopile 1 the active or engineered bioremediation process lasted four years, while biopile 2 was treated passively or non-engineered for eight months. The test species demonstrated varying sensitivity to soils from both biopiles. The effects on test organisms exposed to biopile 2 soils were several times higher compared to those in biopile 1 soils, which correlated with the soil contaminants concentration. Soil hydrocarbon concentrations indeed decreased an average of 81% in biopile 1, whereas in biopile 2 TPH/TPOC concentrations only decreased by 30% after eight months of bioremediation. The bioassays were presented to be sensitive indicators of soil quality and can be used to evaluate the quality of bioremediated soil. The study encourages the need to combine the bioassays with chemical monitoring for evaluation of the bioremediation effectiveness and assessing of the contaminated/remediated soils.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

The chemical and biogenotoxic characterization of organic xenobiotics in aquatic sediment materials 1. The application and comparison of chemically non-specific and biogenotoxic methods

The aim of this work was to evaluate the Ames assay and mixed function oxidase (MFO)-Induct Test used in parallel with chemical group tests (ECD fingerprint and PAH estimation) for the characterization of the organic pollution of water sediment materials. Sediment materials were collected from “clean” and relatively heavily polluted locations in the Middle Adriatic Sea, and from some locations in continental Croatia polluted with wastewaters from different enterprises. Characterization of the organic extracts of the sediment materials investigated was performed chemically using UV spectrofluorometry for the determination polyaromatic hydrocarbons (PAH) and gas chromatography for the determination of volatile EC detector sensitive materials. Genotoxic analysis of the extracts was performed using the MFO-Induct Test and mutagenicity testing using the Standard Plate Incorporation Test as described by Maron and Ames with Salmonella typhimurium TA 98. Measurement of the BaPMO enzyme activity in the livers of carp treated i.p. with total extracts of the sediment investigated confirmed that the methanol extracts generally contained more inducing matter than the petroleum ether extracts. Ames assay showed that for all the samples following the elimination of the sulfur, there was an increase in the number of revertants in comparison to the control number, which indicates that the samples contained mutagenic substances. The larger doses of extracts generally demonstrated cytotoxicity, as evidenced by a reduced number of spontaneous revertants in the Salmonella/Microsome Test. Investigation of the correlation of the chemical parameters with the biological parameter showed that the induction of BaPMO exhibited a statistically significant correlation with the level of the ECD fingerprint of the petroleum ether sediment extract.     

Application of semipermeable membrane device (SPMD) to assess air genotoxicity in an occupational environment

Semipermeable membrane device (SPMD) is a passive sampler that sequesters lipophilic contaminants, mimicking the bioconcentration in the fatty tissue of organisms. This study was designed to assess the use of SPMD and biological tests (Comet assay and Ames test) for air monitoring. For this purpose an occupational environment with expected polycyclic aromatic hydrocarbons (PAHs) contamination (coke plant) was selected for a case study. The SPMDs were deployed in five occupational contaminated sites and in a control site. The SPMD dialysates were chemically analysed and examined for in vitro DNA-damaging activity in human cells (Jurkat) by Comet assay and for mutagenicity with the Ames test (TA98 strain, w/o S9). Total suspended particulates were also collected and analysed (GC–MS). No biological effect of SPMD extract was revealed in the control site. On the other hand, air samples collected with SPMDs within the coke plant showed variable degrees of genotoxic and mutagenic activity. The highest effects were associated with the highest PAH level recovered in the SPMDs extracts and in particulate samples.Results obtained support the sensitivity of biological tests associated to SPMD sampling for evaluating the health risk of potentially contaminated work environments highlighting the usefulness of SPMDs for environmental air quality monitoring.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Acute toxicity and genotoxicity of aquatic hydrophobic pollutants sampled with semipermeable membrane devices

Triolein-filled semipermeable membrane devices (SPMDs) were deployed for 4 weeks in polluted water sources in Lithuania. The mixtures of pollutants sampled by the SPMDs were fractionated by size-exclusion chromatography (SEC). The fraction containing average molecular weight compounds such as polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides was screened by gas chromatography and mass spectrometry. The whole (non-fractionated) samples and their SEC fractions were tested in bioassays including Microtox, Mutatox, Daphnia pulex immobilization assay and the sister chromatid exchange (SCE) in human lymphocytes in vitro test. The Microtox test was most sensitive with the estimated EC(50) values in the range of milligrams or even micrograms per milliliter based on the amount of the SPMD triolein. Part of the observed toxicity was caused by elemental sulfur co-sampled by the SPMDs from sediments. The sum of toxicity equivalents of the SEC fractions was smaller than the relative toxicity of the whole samples indicating the presence of synergistic interactions in the complex mixtures of chemical pollutants. The toxic or genotoxic response induced by the chemical mixtures and their fractions was smaller in the D. pulex, Mutatox and SCE tests. In Mutatox, a positive response was only detected without the S9 metabolic activation which indicates the presence of mainly direct-acting mutagens in the samples. Interpretation of the Mutatox data was difficult due to the complexity of dose-response and time-response relationships. The study has demonstrated the potential as well as some limitations of SPMDs in the monitoring of biological effects of bioavailable organic pollutants in the aquatic environment.     

Petroleum refinery secondary effluent polishing using freezing processes--toxicity and organic contaminant removal

A petroleum refinery secondary effluent was treated using two freezing techniques--spray freezing and unidirectional downward freezing (UDF). The freezing processes were effective to remove toxicity and total organic carbon (TOC)- and chemical oxygen demand (COD)-causing materials in the effluent. Agitation of the liquid during UDF significantly improved the impurity separation efficiency; 85 to 96% removal of TOC and COD was achieved without any pretreatment and freezing only 70% of the feed water. The treatment efficiency of the spray freezing was at the same level as that of UDF without mixing. The spray ice with longer storage time released more contaminants with early meltwater. The initial contaminant concentration of the feed water and the freezing temperatures (-10 degrees C and -25 degrees C) had no significant influence on the treatment efficiency. A small fluctuation in effluent TOC concentration caused a dramatic change in effluent toxicity (Microtox). The effective concentration (EC20) (Microtox) was effective in detecting effluent toxicity.     

Effects of nutrient and temperature on degradation of petroleum hydrocarbons in contaminated sub-Antarctic soil

Mesocosm studies using sub-Antarctic soil artificially contaminated with diesel or crude oil were conducted in Kerguelen Archipelago (49 degrees 21' S, 70 degrees 13' E) in an attempt to evaluate the potential of a bioremediation approach in high latitude environments. All mesocosms were sampled on a regular basis over six months period. Soils responded positively to temperature increase from 4 degrees C to 20 degrees C, and to the addition of a commercial oleophilic fertilizer containing N and P. Both factors increased the hydrocarbon-degrading microbial abundance and total petroleum hydrocarbons (TPH) degradation. In general, alkanes were faster degraded than polyaromatic hydrocarbons (PAHs). After 180 days, total alkane losses of both oils reached 77-95% whereas total PAHs never exceeded 80% with optimal conditions at 10 degrees C and fertilizer added. Detailed analysis of naphthalenes, dibenzothiophenes, phenanthrenes, and pyrenes showed a clear decrease of their degradation rate as a function of the size of the PAH molecules. During the experiment there was only a slight decrease in the toxicity, whereas the concentration of TPH decreased significantly during the same time. The most significant reduction in toxicity occurred at 4 degrees C. Therefore, bioremediation of hydrocarbon-contaminated sub-Antarctic soil appears to be feasible, and various engineering strategies, such as heating or amending the soil can accelerate hydrocarbon degradation. However, the residual toxicity of contaminated soil remained drastically high before the desired cleanup is complete and it can represent a limiting factor in the bioremediation of sub-Antarctic soil.     

Heavy metal in sediments of Ziya River in northern China: distribution,potential risks,and source apportionment

The concentration partitioning between the sediment particle and the interstitial water phase plays an important role in controlling the toxicity of heavy metals in aquatic systems. The aim of this study was to assess the sediment quality in a polluted area of the Ziya River, Northern China. The contamination potential and bioavailability of six metals were determined from the concentrations of total metals and the bioavailable fractions. The results showed that the concentrations of Cr, Cu, Ni, Zn, and Pb exceeded the probable effect concentration at several sites. The high geoaccumulation indices showed that the sediments were seriously contaminated by Cd. The ratio of acid-volatile sulfide (AVS) to simultaneously extracted metal (SEM) was higher than 1, which indicated that the availability of metals in sediments was low. The risk assessment of interstitial waters confirmed that there was little chance of release of metals associated with acid-volatile sulfide into the water column. Values of the interstitial water criteria toxicity unit indicated that none of the concentrations of the studied metals exceeded the corresponding water quality thresholds of the US Environmental Protection Agency. Positive matrix factorization showed that the major sources of metals were related to anthropogenic activities. Further, if assessments are based on total heavy metal concentrations, the toxicity of heavy metals in sediment may be overestimated.     

Removal of chromium and reduction of toxicity to Microtox system from tannery effluent by the use of calcium alginate beads containing humic acid

Removal of chromium (Cr) from tannery effluents by recovery of metal also reduces the ecotoxicological impact. To develop such a process, columns packed with calcium alginate (CA) beads with or without humic acid (HA) have been used as an adsorbent and tannery effluent was passed through it. Concentration of Cr in beads and in different fractions collected after adsorption was measured. Change in total organic carbon content during the process was also noticed. The fractions were also tested for toxicity towards Microtox assay. EC(50) values were determined with the help of Microtox analyser 500. Data showed that the CA beads along with HA could be effectively utilised in removal of 54% Cr and also in reducing the toxicity (EC(50) (%) in 5 min=>100 in fractions collected after 72 h).