Sea-nine antifoulant: an environmentally acceptable alternative to organotin antifoulants

This article reviews previously reported data on the performance, environmental fate, and environmental modeling of Sea-Nine 211 antifoulant (4,5-dichloro-2-n-octyl-4-isothiazolin-3-one). Since organotins are an industry standard, the environmental fate and environmental modeling results of tributyltin (TBT) are compared to those of the Sea-Nine antifoulant for reference. Laboratory and field tests results have shown Sea-Nine antifoulant to be highly effective. Five years of commercial use has confirmed this. Sea-Nine antifoulant and TBT were compared in an environmental risk assessment to predict their effects on the environment. Sea-Nine antifoulant was degraded rapidly in the environment by microorganisms. Its half-life in aerobic and anaerobic microcosm studies was less than 1 h. TBT degraded slowly under aerobic and anaerobic conditions with half-lives ranging from 6 to 9 months. The degradation products of Sea-Nine antifoulant were ring-opened compounds with greatly reduced toxicity. TBT degraded to dibutyltin species, which were still toxic and persistent in the environment. Bioaccumulation studies in fish showed essentially no bioaccumulation of the Sea-Nine biocide. The bioaccumulation of TBT was significant, with bioconcentration factors as high as 10000. The Sea-Nine antifoulant showed no chronic or reproductive toxicity to marine species, while TBT showed a wide range of effects on growth, development, and reproduction at levels as low as 2 parts per trillion (ppt). Computer modeling using the Exposure Analysis Modeling System (EXAMS) predicted maximum concentrations of Sea-Nine biocide of up to 10 ppt, far below the maximum acceptable environmental concentration (MAEC) of 630 ppt. The maximum predicted concentrations of TBT were as high as 345 ppt, far above the UK Environmental Standard in seawater of 2 ppt.     

Developments in biotechnology of relevance to drinking water preparation

This paper discusses strategies to increase the feasibility of microorganisms for the removal of toxic xenobiotics from waste water and drinking water. Based on the principles of adaptational mutations and genetic exchange of catabolic activities, it becomes possible to select and engineer microorganisms that are suitable for the degradation of recalcitrant compounds. The detailed biochemical knowledge that is required for this is now rapidly evolving, and especially for the degradation of chlorinated organics several detoxifying dehalogenation mechanisms have been studied in detail. The feasibility of specialized bacteria for waste and water treatment will be dependent on the possibility to obtain stable performance and maintenance in treatment systems.     

Comparative toxicity of organotin compounds to rainbow trout (Oncorhynchus mykiss) yolk sac fry

The comparative toxicity of various organotin compounds was investigated in early life stages of the rainbow trout. Beginning with yolk sac fry, trout were continuously exposed for 110 days to tributyl- (TBTC), triphenyl- (TPhTC) or tricyclohexyltin chloride (TCHTC) at concentrations of 0.12-15 nM, to trimethyltin chloride (TMTC) at concentrations of 3-75 nM or to dibutyl- (DBTC) or diphenyltin chloride (DPhTC) at 160-4000 nM. The diorganotin compounds DBTC and DPhTC were about three orders of magnitude less toxic than the triorganotin homologs TBTC and TPhTC. Both for DBTC and DPhTC, a no-observable-effect concentration (NOEC) of 160 nM was established, corresponding to 40 and 60 ppb, respectively. Of the triorganotin compounds, TCHTC appeared to be the most toxic, inducing 100% mortality within 1 week at a concentration of 3 nM. Only a few trout survived exposure to 0.6 nM TCHTC for 110 days. TBTC and TPhTC caused acute mortality at a concentration of 15 nM. For both TBTC and TPhTC a NOEC of 0.12 nM was established, corresponding to water concentrations of 40 and 50 ppt, respectively. Histopathological examination revealed depletion of glycogen in liver cells of both di- and triorganotin exposed fish, except in the case of TMTC. No signs of toxicity were observed in fish exposed to up to 75 nM TMTC, the highest concentration tested. Atrophy of the thymus, the most prominent sign of toxicity of di- and tributyltin compounds in mammalian species, was not observed in early life stages of rainbow trout. Tail melanization was observed in the groups exposed to 3 nM TPhTC, 3 nM TBTC, 800 nM DBTC and 800 nM DPhTC. At the end of the exposure period, resistance to infection was examined by an intraperitoneal challenge with Aeromonas hydrophila, a secondary pathogenic bacterium to fish. Resistance of bacterial challenge was found to be decreased even at the lowest-effect concentration of both di- and triorganotin compounds.     

Degradation of microcystin in sediments at oxic and anoxic, denitrifying conditions

The potent toxin microcystin is frequently released during cyanobacterial blooms in eutrophic waters and may impose a risk to human health, when surface water is used for drinking water. For removal of microcystin in surface waters, infiltration through sediment is commonly used. In the present study, mineralization of 14C-labelled microcystin (accumulation of 14CO(2)) and concentration changes (protein phosphatase inhibition assay) demonstrated that indigenous microorganisms in the sediment of a water recharge facility were capable of degrading microcystin. At oxic or microaerophilic (<2% O(2)) conditions, microcystin added to sediment slurries at 70 microg l(-1) was reduced to <20 microg l(-1) in 1-2 weeks, and less than 3 microg l(-1) after 7 weeks. At anoxic conditions (<0.3% O(2)) and with addition of nitrate, the degradation was significantly stimulated, reducing microcystin from 100 to <20 microg l(-1) within 1 day. The simultaneous production of N(2)O in the samples suggests that the microcystin degradation was coupled to dissimilative nitrate reduction (denitrification). Since aquifers and sediments beneath drinking water reservoirs often are anoxic, nitrate respiration may be an important process in removal and detoxification of microcystin.     

Microcosm investigations of phthalate behaviour in sewage treatment biofilms

Discharge from sewage works has been shown to be an important source of phthalates into the environment which is of major concern because some are toxic, suspected endocrine disruptors and recalcitrant. Laboratory trickle filter microcosms (continuous and re-circulating flow) were constructed and operated to investigate the biodegradation and adsorption of phthalates and also to isolate phthalate degrading microorganisms. It was found that adsorption was critical for the removal of both DEP (77.5%) and DEHP (55.7%) in continuous flow microcosms. The proportion of phthalates removed by biodegradation in the continuous flow microcosms was estimated. Re-circulating flow microcosms improved the removal of DEHP compared to continuous flow microcosms. Microcosm biofilm used for an enrichment culture on phthalate media isolated a varied group of microbes including Gram negative and Gram positive bacteria, yeasts and fungi. Bacteria species with all the necessary enzymes to degrade phthalic acid were isolated.     

Fate of organotins in sewage sludge during anaerobic digestion

Adsorption onto sewage sludge is an important process for the elimination of tributyltin (TBT) from wastewater. However as the disposal of sewage sludge to agricultural land is a significant route for recycling biosolids, there exists an issue as to whether the potential long-term build-up of organotins in agricultural soil is acceptable, from a human health and environmental point of view. For the sustainable use of biosolids in agriculture it is essential to control and reduce the quantities of persistent pollutants such as organotins in sewage sludge. In this study, a sampling program was designed to establish the levels of TBT (and other organotins) in sewage sludge and their reduction during anaerobic treatment and processing prior to disposal. Experiments were also undertaken to assess the fate of TBT in laboratory scale anaerobic digesters where the influence of digester operating parameters could be evaluated. Organotin concentrations were determined using capillary gas chromatography with flame photometric detection. The results demonstrated that the majority of TBT remained concentrated in the solid phase (sewage sludge). Concentrations of TBT in sewage sludge were approximately 18 mg kg(-1) (dry weight) and both laboratory experiments and fieldwork demonstrated that degradation of TBT during anaerobic digestion of sludge was minimal.     

TBT in marine sediments and blue mussels (Mytilus edulis) from central-west Greenland

Concentrations of butyltin compounds were investigated in the bivalve Mytilus edulis (five sites) and marine sediments (three sites) near the largest town, Nuuk, in Greenland. In seven of the eight samples the extremely toxic compound tributyltin (TBT) was detected. The concentrations of tributyltin and degradation products in the bivalves were close to 1 microgram kg-1 wet weight (ww), calculated as Sn, which is lower than those found in Iceland and the Faeroe Islands. In sediments the concentration of TBT ranged from below the limit of detection of 1 microgram kg-1 to 171 micrograms kg-1 dry weight (dw), calculated as Sn, which is comparable to levels found in Europe.     

Toxicity to Daphnia magna and Vibrio fischeri of Kraft bleach plant effluents treated by catalytic wet-air oxidation

Two Kraft-pulp bleaching effluents from a sequence of treatments which include chlorine dioxide and caustic soda were treated by catalytic wet-air oxidation (CWAO) at T=463 K in trickle-bed and batch-recycle reactors packed with either TiO2 extrudates or Ru(3 wt%)/TiO2 catalyst. Chemical analyses (TOC removal, color, HPLC) and bioassays (48-h and 30-min acute toxicity tests using Daphnia magna and Vibrio fischeri, respectively) were used to get information about the toxicity impact of the starting effluents and of the treated solutions. Under the operating conditions, complex organic compounds are mostly oxidized into carbon dioxide and water, along with short-chain carboxylic acids. Bioassays were found as a complement to chemical analyses for ensuring the toxicological impact on the ecosystem. In spite of a large decrease of TOC, the solutions of end products were all more toxic to Daphnia magna than the starting effluents by factors ranging from 2 to 33. This observation is attributed to the synergistic effects of acetic acid and salts present in the solutions. On the other hand, toxicity reduction with respect to Vibrio fischeri was achieved: detoxification factors greater than unity were measured for end-product solutions treated in the presence of the Ru(3 wt%)/TiO2 catalyst, suggesting the absence of cumulative effect for this bacteria, or a lower sensitivity to the organic acids and salts. Bleach plant effluents treated by the CWAO process over the Ru/TiO2 catalyst were completely biodegradable.     

Xenobiotic organic compounds in leachates from ten Danish MSW landfills--chemical analysis and toxicity tests

A monitoring program comprising chemical analysis and biological toxicity testing of leachate samples from 10 Danish landfills (six engineered and four uncontrolled) revealed the presence of 55 different xenobiotic organic compounds (XOCs) and 10 degradation products of XOCs. The compounds belong to the following groups: BTEX, C3-benzenes, bicyclo compounds, napthalenes, chlorinated aliphatics, phenols (chloro-, methyl-, dimethyl, nonyl-), pesticides, and phthalates. Concentrations of single XOCs ranged from <0.1 to 2220 microg/L. A pesticide screening including 101 different compounds resulted in detection of 18 pesticides and three degradation products. The findings of degradation products of toluene, phenols, phthalates, pesticides, and nonylphenol ethoxylates show that degradation occurred inside the landfills. In biotests with bacteria and algae it was found that the non-volatile organic compounds were toxic as the samples only needed to be pre-concentrated from 1.3 to 9.4 times to give 50% inhibition of the test organisms. One of the ten samples proved to be genotoxic in the umuC test after 141 times pre-concentration. A major part of the organic chemicals causing toxicity remains unknown and it is recommended to combine chemical analyses and biotests in future monitoring programs.     

Solar driven production of toxic halogenated and nitroaromatic compounds in natural seawater

Natural seawater (NSW) sampled in March and June 2007 in the Gulf of Trieste, Italy, has been spiked with phenol and irradiated in a device simulating solar light spectrum and intensity. Opposite to the case of artificial seawater, for which phenol is slightly degraded by direct photolysis, in NSW the phenol degradation mediated by natural photosensitizers occurs, forming several secondary pollutants, including hydroxyderivatives (1,4-benzoquinone, resorcinol), three chlorophenol isomers, 2,3-dichlorophenol, 2- and 4-bromophenol, 2- and 4-nitrophenol, and several condensed products (2 and 4-phenoxyphenol, 2,2'-, 4,4'- and 2,4-bisphenol). These compounds are toxic to bacteria and other living organisms. Ecotoxicologic effect has been evaluated by using the Vibrio Fischeri luminescent bacteria assay. This technique uses marine organisms, and it is therefore well suited for the study on marine samples. A correlation exists between the intermediates evolution and the toxicity profile, as the largest toxicity is observed when compounds with the lower EC50 (halophenols, phenoxyphenols) are formed at higher concentration.     

Toxicity and bioaccumulation of tributyltin and triphenyltin on oysters and rock shells collected from Taiwan maricuture area

The present study was undertaken to evaluate the toxicity of tributyltin (TBT) on oysters (Crassostrea gigas) and bioaccumulation of TBT and triphenyltin (TPhT) on oysters and rock shells (Thais clavigera) from mariculture areas of Taiwan. When treated with concentrations of 0.08, 0.40, 2.00, 10.00 and 50.00 microg TBT/L, the 48-, 72-, 96- and 120-h LC50s of oysters were 44.6, 18.4, 17.9 and 14.3 microg TBT/L, respectively. In the bioaccumulation experiments, oysters and rock shells were exposed to various concentrations of organotins, i.e. A: control, B: 0.40 microg TBT/L, C: 0.40 microg TPhT/L, and D: 0.20 microg TBT/L + 0.20 microg TPhT/L. In general, TPhT was faster accumulated than TBT in both oysters and rock shells and oysters had a higher elimination capability than rock shells. Additionally, greater bioaccumulation and elimination rates had been observed in female oysters than males. To rock shells, the bioaccumulation rate of organotins in imposex females was greater than males and females.     

Microorganisms and particles in AHU systems: Measurement and analysis

In this study, for better understanding the practical removal effect of air handling unit (AHU) system on airborne microorganisms (including bacteria and fungus) and particles and microbial growth, the samples of microorganisms and particles in 10 air handling unit (AHU) systems including fan coils and indoor air were collected and analyzed in air and component surfaces of such systems in two large public buildings. It is found that the removal efficiency is of the highest for bacteria 73.9% and the lowest for particles (0.5–2 μm) 24.4%. The surface concentration of equipment bacteria is 29 CFU/cm² and fungi 137 CFU/cm². Five of 10 systems have higher fungi concentrations on air intake than that on diffuser. The results also show that the central air supply system with common components (e.g., pre-filter and bag filter) has difficulty to achieve/maintain good performance once microorganisms and particles exist, especially for particle size D ≤ 3.3 μm. The size distribution has large influence on removal efficiency. The microbial growth on surfaces of duct and equipment was noticed and may be transferred into indoor air. This will decrease the indoor air quality and lead to adverse health effect.     

Microbial toxicity of metal oxide nanoparticles (CuO, NiO, ZnO, and Sb2O3) to Escherichia coli, Bacillus subtilis, and Streptococcus aureus

In this study, the microbial toxicities of metal oxide nanoparticles were evaluated for Escherichia coli, Bacillus subtilis, and Streptococcus aureus in laboratory experiments. The nanoparticles tested were CuO, NiO, ZnO, and Sb₂O₃. The metal oxide nanoparticles were dispersed thoroughly in a culture medium, and the microorganisms were cultivated on Luria-Bertani agar plates containing different concentrations of metal oxide nanoparticles. The bacteria were counted in terms of colony forming units (CFU). The CFU was reduced in a culture medium containing metal oxide NP, and the dose-response relationship was characterized. CuO nanoparticles were found to be the most toxic among the tested nanoparticles, followed by ZnO (except S. aureus), NiO, and Sb₂O₃ nanoparticles. We determined that the intrinsic toxic properties of heavy metals are also associated with the toxicity of metal oxide nanoparticles. Ion toxicity was also evaluated to determine the effects of metal ions dissolved from metal oxide NPs, and the toxicity induced from the dissolved ions was determined to be negligible herein. To the best of our knowledge, this is the first study of the toxicity of NiO and Sb₂O₃ NPs on microorganisms. We also discuss the implications of our findings regarding the effects of the intrinsic toxic properties of heavy metals, and concluded that the apparent toxicities of metal oxide NPs can largely be understood as a matter of particle toxicity.     

Biodegradation potential of pure and mixed bacterial cultures for removal of 4-nitroaniline from textile dye wastewater

Environmentally toxic aromatic amines including nitroanilines are commonly generated in dye contaminated wastewater in which azo dyes undergo degradation under anaerobic conditions. The aim of this study was to develop a process for biological treatment of 4-nitroaniline. Three bacteria identified as Acinetobacter sp., Citrobacter freundii and Klebsiella oxytoca were isolated from enrichment cultures of activated sludge on 4-nitroaniline, after which the isolates and the mixed culture were studied to determine optimal conditions for biodegradation. HPLC analyses showed the mixed culture was capable of complete removal of 100 μmol/L of 4-nitroaniline within 72 h under aerobic conditions. There was an inverse linear relationship (R² = 0.96) between the rate of degradation (V) and 4-nitraoaniline concentrations [S] over 100-1000 μmol/L. The bacterial culture was also capable of decolorizing structurally different azo dyes (Acid Red-88, Reactive Black-5, Direct Red-81, and Disperse Orange-3) and also degraded nitrobenzene. Our findings show that enrichment cultures from activated sludge can be effective for the removal of dyes and their toxic intermediates, and that treatment may best be accomplished using an anaerobic-aerobic process.     

Microorganisms in bioaerosol emissions from wastewater treatment plants during summer at a Mediterranean site

Measurements were conducted at a Mediterranean site (latitude 35 degrees 31' north and longitude 24 degrees 03' east) during summer, to study the concentration of microorganisms emitted from a wastewater treatment plant under intensive solar radiation (520-840 W/m2) and at elevated air temperatures (25-31 degrees C). Air samples were taken with the Air Sampler MAS 100 (Merck) at each stage of an activated-sludge wastewater treatment (pretreatment, primary settling tanks, aeration tanks, secondary settling tanks, chlorination, and sludge processors). Cultivation methods based on the viable counts of mesophilic heterotrophic bacteria, as well as of indicator microorganisms of faecal contamination (total and faecal coliforms and enterococci), and fungi were performed. During air sampling, temperature, solar radiation, relative humidity and wind speed were measured. The highest concentrations of airborne microorganisms were observed at the aerated grit removal of wastewater at the pretreatment stage. A gradual decrease of bioaerosol emissions was observed during the advanced wastewater treatment from the pretreatment to the primary, secondary and tertiary treatment (97.4% decrease of mesophilic heterotrophic bacteria, and 100% decrease of total coliforms, faecal coliforms and enterococci), 95.8% decrease of fungi. The concentration of the airborne microorganisms at the secondary and tertiary treatment of the wastewater was lower than in the outdoor control. At the same time, the reduction of the microbial load at the waste sludge processors was 19.7% for the mesophilic heterotrophic bacteria, 99.4% for the total coliforms, and 100% for the faecal coliforms and the enterococci, 84.2% for the fungi. The current study concludes that the intensive solar radiation, together with high ambient temperatures, as well as optimal wastewater treatment are the most important factors for low numbers of microbes in the air.     

Reduction of phenol content and toxicity in olive oil mill waste waters with the ligninolytic fungus Pleurotus ostreatus

Olive oil mill waste waters (OMW) constitute a major environmental problem because of the large amount produced and the toxicity of the phenolic compounds present. Several of these aromatic compounds can be assimilated to many of the components of lignin. Only few microorganisms, mainly “white-rot” basidiomycete, are able to degrade lignin by means of oxidative reactions catalysed by phenol oxidases and peroxidases.Both the low degree of specificity which characterizes these enzymes, and the structural relationships of many aromatic pollutants with the natural substrates of the enzymes, have suggested the use of ligninolytic organisms and of their enzymes for the treatment of these kinds of substrates.This paper investigates the ability of the “white-rot” basidiomycete Pleurotus ostreatus and particularly of the phenol oxidases it produces in the detoxification of OMW phenol compounds.Treatment of OMW with purified phenol oxidase showed a significant reduction of phenolic content, but no decrease of its toxicity was observed when tested on Bacillus cereus. Otherwise, the effect of processing OMW with the entire microorganism resulted in a noticeable detoxification of the waste with concomitant abatement of the phenol content.     

Toxicity of chlorpyrifos and TCP alone and in combination to Daphnia carinata: the influence of microbial degradation in natural water

The acute toxicity of chlorpyrifos and its principal metabolite 3,5,6-trichloropyridinol (TCP) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. TCP was found to be more toxic than its parent chemical chlorpyrifos to Daphnia survival in cladoceran culture medium. However, TCP in natural water was not toxic to D. carinata up to 2 microgL(-1). The LC(50) values for chlorpyrifos, TCP and chlorpyrifos+TCP were 0.24, 0.20 and 0.08 microgL(-1), respectively, in cladoceran culture medium. Although the parent chemicals and their degradation products co-exist in natural waters, the existing guidelines for water quality are based on individual chemicals. The results of this investigation suggest that chlorpyrifos and TCP can interact synergistically, additively or antagonistically, resulting in an increase or decrease in the overall toxicity of the mixture compared to individual compounds. The indigenous microorganisms in natural water could play a significant role in degradation of these compounds thereby influencing their toxicity in receiving waters. This study clearly suggests that the joint action of pesticides and their degradation products should be considered in the development of water quality guidelines. To our knowledge, this is the first study on the interactive effect of chlorpyrifos and TCP to a cladoceran and suggests that these two compounds are non-toxic when present together at concentrations up to 0.12 microgL(-1). However, these compounds together act additively at and above 0.5 microgL(-1) to fresh water invertebrates and therefore pollution with these compounds may adversely affect natural ecosystems.     

Microbial degradation of cyanobacterial cyclic peptides

Bacterial strain B-9 possesses hydrolytic enzymes capable of degrading microcystins (MCs) and nodularin that are toxic cyclic peptides produced by cyanobacteria. In the present study, the degradation activities of the cell extract of B-9 against non-toxic cyanobacterial cyclic peptides other than the MCs and nodularin were investigated, and the degradation products were analyzed by liquid chromatography/ion trap tandem mass spectrometry (LC/ITMS). It was confirmed that B-9 could also degrade these cyanobacterial cyclic peptides by hydrolysis of their peptide bonds. These results indicated that this bacterium possesses a very unique hydrolytic activity that can degrade structurally different cyclic peptides and that this may be effective for the detoxification of hazardous cyclic peptides.     

Toxicity of benzotriazole and benzotriazole derivatives to three aquatic species

Benzotriazole and its derivatives comprise an important class of corrosion inhibitors, typically used as trace additives in industrial chemical mixtures such as coolants, deicers, surface coatings, cutting fluids, and hydraulic fluids. Recent studies have shown that benzotriazole derivatives are a major component of aircraft deicing fluids (ADFs) responsible for toxicity to bacteria (Microtox). Our current research compared the toxicity of benzotriazole (BT), two methylbenzotriazole (MeBT) isomers, and butylbenzotriazole (BBT). Acute toxicity assays were used to model the response of three common test organisms: Microtox bacteria (Vibrio fischeri), fathead minnow (Pimephales promelas) and water flea (Ceriodaphnia dubia). The response of all the three organisms varied over two orders of magnitude among all compounds. Vibrio fischeri was more sensitive than either C. dubia or P. promelas to all the test materials, while C. dubia was less sensitive than P. promelas. The response of test organisms to unmethylated benzotriazole and 4-methylbenzotriazole was similar, whereas 5-methylbenzotriazole was more toxic than either of these two compounds. BBT was the most toxic benzotriazole derivative tested, inducing acute toxicity at a concentration of < or = 3.3 mg/l to all organisms.     

Degradation of pharmaceuticals in non-sterile urban wastewater by Trametes versicolor in a fluidized bed bioreactor

The constant detection of pharmaceuticals (PhACs) in the environment demonstrates the inefficiency of conventional wastewater treatment plants to completely remove them from wastewaters. So far, many studies have shown the feasibility of using white rot fungi to remove these contaminants. However, none of them have studied the degradation of several PhACs in real urban wastewater under non-sterile conditions, where mixtures of contaminants presents at low concentrations (ng L⁻¹ to μg L⁻¹) as well as other active microorganisms are present. In this work, a batch fluidized bed bioreactor was used to study, for the first time, the degradation of PhACs present in urban wastewaters at their pre-existent concentrations under non-sterile conditions. Glucose and ammonium tartrate were continuously supplied as carbon and nitrogen source, respectively, and pH was maintained at 4.5. Complete removal of 7 out of the 10 initially detected PhACs was achieved in non-sterile treatment, while only 2 were partially removed and 1 of the PhACs analyzed increased its concentration. In addition, Microtox test showed an important reduction of toxicity in the wastewater after the treatment.