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Hazardous substances data bank (HSDB) as a source of environmental fate information on chemicals.

The Hazardous Substances Data Bank (HSDB), a factual data bank on the National Library of Medicine's (NLM) TOXNET (Toxicology Data Network) online system, provides information in areas such as chemical substance identification, chemical and physical properties, safety and handling, toxicology, pharmacology, environmental fate and transformation, regulations, and analytical methodology. This article discusses how environmental fate data is handled in HSDB.

Animals↗

Biological chromium(VI) reduction using a trickling filter.

A pilot-scale trickling filter was constructed and tested for biological chromium(VI) removal from industrial wastewater. Indigenous bacteria from industrial sludge were enriched and used as inoculum for the filter. Sodium acetate was used as carbon source and it was found to inhibit chromate reduction at high concentrations. Three different operating modes were used to investigate the optimal performance and efficiency of the filter, i.e. batch, continuous and SBR with recirculation. The latter one was found to achieve removal rates up to 530 g Cr(VI)/m2 d, while aeration was taking place naturally without the use of any external mechanical means. The low operating cost combined with the high hexavalent chromium reduction rates indicates that this technology may offer a feasible solution to a very serious environmental problem.

Biodegradation, Environmental↗

Biodesulfurization.

Microbial sulfur-specific transformations have been identified that selectively desulfurize organic sulfur compounds in fossil fuels. Recent discoveries related to biodesulfurization mechanisms may lead to commercial applications of biodesulfurization through engineering recombinant strains for over-expression of biodesulfurization genes, removal of end product repression, and/or by combining relevant industrial and environmental traits with improvements in bioprocess design.

Bacteria↗

Fast quantification of humic substances and organic matter by direct analysis of sediments using DRIFT spectroscopy.

A simple method based on diffuse reflectance coupled with infrared Fourier transform spectroscopy (DRIFTS) has been developed for the quantification and the characterization of sedimentary (or soil, peat, etc.) humic substances. Under optimized conditions, the quantification of humic substances or total organic matter is possible with DRIFTS at a frequency of 2930 cm(-1) using whole dry sediment samples. A study of the operational parameters that affect the DRIFTS signal shows the importance of normalizing analysis conditions, especially the diffuse reflectance accessory alignment, the particle size and compaction, and the homogeneity of the powdered samples, to obtain reproducible quantitative analyses. The quantification of total humic substances by DRIFTS correlates well with the concentrations determined using classical extraction methods. DRIFTS analysis requires only a few minutes instead of tedious extractions of humic substances. Moreover, the distribution of total organic matter and of fulvic acids, humic acids, and humin can also be obtained. Analysis of natural samples indicates that a calibration using humic material representative of the studied area provides the most accurate quantification. The fast screening of organic matter fractions by DRIFTS on intact natural samples provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.

Algorithms↗

Biosorption and solubilization of copper oxychloride fungicide by Aspergillus niger and the influence of calcium.

The biosorption of copper oxychloride fungicide particulates (approximately 1 microm diameter), at concentrations ranging from 25 to 500 ppm active ingredient (ai), by pelleted mycelium of Aspergillus niger grown on Czapek Dox medium was evaluated. The concentration of the fungicide adsorbed to the mycelium, remaining suspended or solubilized in the medium, was determined by analysis of its copper content (CuF) using atomic absorption spectrophotometry (AAS). 2-day-old pellets exhibited high biosorption efficiency ranging from 97 +/- 1.0 to 88 +/- 1.2% of the initially added fungicide concentrations, respectively, within 10 min. However, under the same conditions, amounts of the removed fungicide by 6-day-old mycelial pellets were significantly lower and ranged from 0.5 +/- 0.03 to 0.15 +/- 0.01%. Scanning electron microscopy studies of 2-day-old pellets supplemented with the fungicide revealed predominant aggregations of clumps and dense particulates on the hyphal tips. The adsorbed CuF of 125 ppm ai fungicide subsequently decreased from 7.5 +/- 0.5 to 2.1 +/- 0.1 micromol Cu (mg dry wt)(-1) after 12 h incubation. Simultaneously, the soluble portion of CuF remaining in the medium increased from 0.9 +/- 0.6 to 4.9 +/- 0.2 micromol Cu ml(-1). The presence of 50 mM CaCl2 resulted in a decrease of the adsorbed CuF to 3.5 +/- 0.5 micromol Cu (mg dry wt)(-1) and solubilized copper in the medium increased to 5.9 +/- 0.8 micro mol Cu ml(-1). Additionally, the cellular copper contents attained after 2 h were 0.08 +/- 0.01 and 0.16 +/- 0.007 micromol Cu (mg dry wt)(-1) in absence and presence of calcium, respectively. The addition of calcium to glucose-starved pellets greatly increased the medium [H+] which was conclusively discussed in relation to Ca2+/H+ exchange capacity of the fungal cells. These results are of potential environmental, biotechnological and agricultural importance.

Absorption↗

Use of a novel plasmid to monitor the fate of a genetically engineered Pseudomonas putida strain.

Plasmid pSI30 was constructed to increase the sensitivity of detection of a genetically engineered micro-organism (GEM) and its recombinant DNA in environmental samples. This broad host-range, mobilizable plasmid contained chlorocatechol (clc) degradative genes, antibiotic resistance genes (ampicillin and kanamycin) and a fragment of eukaryotic DNA. The clc genes encode enzymes that convert 3-chlorocatechol to maleylacetic acid permitting the host, Pseudomonas putida RC-4, to grow on 3-chlorobenzoate. This catabolic phenotype was exploited using enrichment procedures to detect RC-4(pSI30) cells, free-living in the water column or when irreversibly bound to surfaces. The eukaryotic DNA sequence provided a unique target allowing positive identification by DNA:DNA hybridization. Using the eukaryotic DNA sequence as a probe, no transfer of the plasmid to indigenous bacteria was detected. Persistence of RC-4(pSI30) and its ability to multiply upon addition of 3-chlorobenzoate were demonstrated 78 days after its addition to natural freshwater. In flow-through microcosms RC-4(pSI30), undetectable as free-living cells, was found by enrichment as irreversibly bound sessile forms. These experiments revealed the stability of pSI30 and its utility in a 'combination' detection system for tracking the survival of a GEM and its DNA in environmental samples.

Biodegradation, Environmental↗

Phase I xenobiotic metabolic systems in plants.

Phytoremediation uses living higher plants for the removal and biochemical decomposition of environmental pollutants. In this paper Phase I metabolic pathways in the biotransformation reactions of organic pollutants in plants are reviewed. These reactions result in the introduction of functional groups in the xenobiotic molecule or the exposure of preexisting functional groups and lead to the formation of more polar, more water-soluble, chemically more reactive and sometimes biologically more active derivatives. Phase I type reactions are most important in the phytoremediation of hydrophobic, chemically stable organic pollutants, such as polycyclic aromatic hydrocarbons and (poly)chlorinated aliphatic and aromatic hydrocarbons. Although Phase I reactions involve a wide range of chemical transformations from hydrolysis to reduction, oxidative processes catalyzed by cytochrome P450 containing monooxygenases are the most important. Transgenic plants with tailored Phase I enzymatic activities may play major roles in the removal of environmentally stable organic pollutants from contaminated fields.

Biodegradation, Environmental↗

Environmental risk assessment for trisodium [S,S]-ethylene diamine disuccinate, a biodegradable chelator used in detergent applications.

Environmental safety data are presented for [S,S]-Ethylene Diamine Disuccinate ([S,S]-EDDS), a new, biodegradable, strong transition metal chelator. An environmental risk assessment for its use in detergent applications, which takes into account the chelating properties of [S,S]-EDDS, is proposed. A property of [S,S]-EDDS that distinguishes it from other strong transition metal chelators is its, "ready" and transparent (no recalcitrant metabolites) biodegradation profile. Because its sorption to activated sludge solids is low (Kp of 40 l/kg), removal of [S,S]-EDDS during sewage treatment, which is greater than 96% as determined by the Continuous Activated Sludge test, is mainly ascribed to biodegradation. At projected use volumes in detergent applications [S,S]-EDDS predicted steady-state concentration in rivers leaving the mixing zone will be below 5 micrograms/l due to rapid biodegradation. [S,S]-EDDS exhibits low toxicity to fish and Daphnia (both EC50S > 1000 mg/l). By contrast, due to limitation of the algal test for chelators apparent toxicity was observed (EC50 = 0.290 mg/l, NOEC--No observable Effect Concentration = 0.125 mg/l). Schowanek et al. [1] demonstrated that this is not toxicity sensu stricto but a chelation effect of trace metals in the test medium and of resulting essential nutrients limitation. This requires specific attention when the results of algal toxicity are to be extrapolated to a field situation to perform realistic risk assessment. Metal speciation calculations, using MINEQL+, show that at the predicted environmental concentrations of [S,S]-EDDS (1-5 micrograms/l), such a chelation effect would be insignificant. These calculations allow to estimate the NOEC for chelation effects in the field to be in the range of 0.250-0.500 mg/l, depending on the background water chemistry. These values are well above the laboratory NOEC. An environmental risk assessment was performed using the EUSES (1.0) program. EUSES is currently the EU recommended tool for conducting risk assessments (TGD 1995). It was applied to estimate the river water and soil concentrations from production, formulation and private use life stages. The estimated PEC/PNEC ratio in all relevant environmental compartments is smaller than 1, indicating "no immediate concern" at the anticipated usage level.

Animals↗

Nonylphenol ethoxylates, but not nonylphenol, are substrates of the human multidrug resistance P-glycoprotein.

Alkylphenol ethoxylates are surfactants that are commonly used in industry and in home care products. They are broken down by anaerobes to yield toxic environmental pollutants such as nonylphenol. In this study, we tested whether nonylphenol ethoxylates and their most common biodegradation product, nonylphenol, were substrates of human P-glycoprotein. In vivo and in vitro assays showed that the enzyme interacts with a wide variety of nonylphenol ethoxylate compounds, but not with nonylphenol. These results suggest that P-glycoprotein can protect organisms from the toxic and estrogenic effects of nonylphenol ethoxylates, but not from the major biodegradation product, nonylphenol.

ATP Binding Cassette Transporter, Subfamily B, Mem↗

Biological and photochemical degradation rates of diethylenetriaminepentaacetic acid (DTPA) in the presence and absence of Fe(III).

The environmental fate of ethylenediaminetetraacetic acid (EDTA) has been extensively studied, while much less is known about the environmental behaviour of diethylenetriaminepentaacetic acid (DTPA). In this study, it was confirmed that DTPA is persistent toward biodegradation. The biodegradability of DTPA was investigated in the absence and in the presence of Fe(III) by using CO2 evolution test and Manometric respirometry test. The CO2 evolution and oxygen uptake of iron-free (DTPA was added as free acid) and Fe(III)DTPA were less than in inoculum blank. Possible inhibitor effect was analysed by testing biodegradation of sodium benzoate with and without iron-free or Fe(III)DTPA in the Manometric respirometry test. Only slight inhibition was observed when DTPA was added as free acid. Photodegradation of iron-free DTPA and Fe(III)-DTPA complex was studied by using sunlight and UV radiation at the range 315-400 nm emitted by black light lamps. The results indicate that DTPA added as free acid degrades photochemically in humic lake water. Fe(III)DTPA was shown to be very photolabile in humic lake water in the summer; the photochemical half-life was below one hour. Photodegradation products were identified by the mass spectrometric technique (GC-MS). It was shown that photodegradation of Fe(III)DTPA does not result in total mineralization of the compound. Diethylenetriaminetetraacetic acid, diethylenetriaminetriacetic acid, ethylenediaminetriacetic acid, N,N'- and/or N,N-ethylenediaminediacetic acid, iminodiacetate, ethylenediaminemonoacetic acid and glycine were identified as photodegradation products of Fe(III)DTPA. Based on these observations, we propose a photodegradation pathway for Fe(III)DTPA.

Biodegradation, Environmental↗

A strain isolated from gas oil-contaminated soil displays chemotaxis towards gas oil and hexadecane.

In this report we describe the isolation of a strain from soil contaminated with gas oil by taking bacteria from a chemotactic ring on gas oil-containing soft agar plates. Partial 16 S rDNA sequencing of the isolated strain showed 99.1% identity with Flavimonas oryzihabitans. It was not only able to degrade different aliphatic hydrocarbons but it was also chemotactic towards gas oil and hexadecane, as demonstrated by the use of three different chemotaxis methods, such as agarose plug and capillary assays and swarm plate analysis. In addition, the strain was chemotactic to a variety of carbon sources that serve as growth substrates, including glucose, arabinose, mannitol, glycerol, gluconate, acetate, succinate, citrate, malate, lactate and casaminoacids. This is the first report on chemotaxis of a hydrocarbon-degrading bacterium towards a pure alkane, such as hexadecane. The fact that environmental isolates show chemotaxis towards contaminant/s present in the site of isolation suggests that chemotaxis might enhance biodegradation by favouring contact between the degrading microorganism and its substrate.

Alkanes↗

Chromium-tolerant bacteria isolated from industrial effluents and their use in detoxication of hexavalent chromium.

Three bacterial strains were isolated from effluents of leather (CMBL Cr13, CMBL Cr14) and steel (CMBL Cr15) industries for their possible use in chromium(VI) detoxication of industrial waste. CMBL Cr13 was found to tolerate chromium(VI) up to a concentration of 45 g/L in the medium, while CMBL Cr14 and CMBL Cr15 could tolerate up to 40 g/L. These bacteria were also checked for resistance to other metals. They resisted a lead concentration of 1 g/L and cadmium concentration of 550 mg/L in the medium. They showed optimum growth at pH 7.3-7.5 at a temperature of 35-37 degrees C. CrVI-reducing ability of the three strains ranged from 70 to 80% after 3 d of incubation. The possible use of these bacteria in environmental cleanup is discussed.

Biodegradation, Environmental↗

Surfactant activity of a naphthalene degrading Bacillus pumilus strain isolated from oil sludge.

We studied the growth, biosurfactant activities and petroleum hydrocarbon compounds utilisation of strain 28-11 isolated from a solid waste oil. The isolate was identified as Bacillus pumilus. It grew well in the presence of 0.1% (w/v) of crude oil and naphthalene under aerobic conditions and utilised these substances as carbon and energy source. The capacity of strain 28-11 to emulsify crude oil and its ability to remove hydrocarbons looks promising for its application in environmental technologies.

Bacillus↗

Composite films based on biorelated agro-industrial waste and poly(vinyl alcohol). Preparation and mechanical properties characterization.

As a part of an ongoing project on the production of composite materials based on poly(vinyl alcohol) (PVA) and polymeric materials from renewable resources, the present paper reports on the incorporation of agricultural waste materials as organic fillers in a film matrix based on PVA as continuous phase. In this study lignocellulosic fibers byproducts, derived from sugar cane (SC) and apple (AP) and orange (OR) fruit juice extraction, were cast from PVA aqueous solutions. The effect of fiber type and composition on the relative properties of cast films was evaluated and compared. OR resulted to be suitable for blending in higher amounts by weight than SC and AP. Glycerol and urea were added as plasticizing agents and were observed to be effective in giving flexible films. Additionally, cornstarch was added to further increase the composition of polymers from renewable resources in cost-effective and ecoefficient composite film formulations. The prepared films resulted sensitive to moisture and water. To reduce water sensitivity, hexamethoxymethylmelamine (HMMM) was tested as a cross-linking agent for the present composite formulations. Cross-linked films exhibited significant improvement in water-resistance that can be taken as a tuneable structural feature for customized applications. The mechanical properties of the prepared composite films (elongation at break, tensile strength, Young modulus) were found to be dependent upon the nature and content of the filler and on environmental conditions.

Agriculture↗

Degradation of racemic and enantiopure metalaxyl in tropical and temperate soils.

The degradation of the racemic mixture and the enantiomers of metalaxyl in typical soils from Germany and Cameroon has been studied. Formulated and unformulated R-metalaxyl were studied as well as racemic (rac) metalaxyl in controlled incubation experiments. The kinetics of the degradation or transformation were determined by means of reversed phase HPLC, while the enantiomeric ratios were measured by HPLC with a chiral Whelk O1 column. The degradation followed first-order kinetics (R2 > or = 0.96). Higher metalaxyl acid metabolite concentrations were found in German soil than in Cameroonian soil. The enantiomers of the fungicide each had different degradation rates in both soils, with half-lives ranging from 17 to 38 days. All forms of metalaxyl had lower degradation rates in the Cameroonian soil than in the German soil. The degradation. of the R-enantiomer was much faster than the S-enantiomer in the German soil and slower than the S-enantiomer in the Cameroonian soil suggesting that different microbial populations, which may be using different enzymes, have different degradation preferences. The results for the major differences in the degradation of the enantiomers may have some implication for the frequency of use as well as the environmental assessment for chiral pesticides.

Alanine↗

Are neutral chloroacetamide herbicide degradates of potential environmental concern? Analysis and occurrence in the upper Chesapeake Bay.

Although laboratory studies have revealed that many different neutral degradates of chloroacetamide herbicides can form during thermochemical, biological, and photochemical transformations, relatively few have been sought in the environment, despite their likely generation in appreciable amounts, relative persistence, and known or potential toxicity. The present paper describes a GC/ MS method for the analysis of 20 neutral chloroacetamide degradates, along with the four parent compounds, three triazine herbicides, and two neutral triazine degradates. Using large volume injections and 300:1 concentration via solid phase extraction, detection limits for most neutral chloroacetamide degradates were in the hundreds of pg/L range (low ng/L range for degradates possessing a hydroxy group). In a depth profile taken in midsummer from the upper Chesapeake Bay, 19 of the 20 neutral chloroacetamide degradates of interest were detected, along with three ionic oxanilic acid derivatives. Of those degradates encountered, eight do not appear to have been previously reported in natural or affected environmental samples. Concentrations of most neutral chloroacetamide degradates exceeded those of the parent compounds, while the total concentration of the neutral chloroacetamide degradates was 20-30 times that of the parents. These micropollutants therefore merit more detailed attention as contaminants of potential environmental concern.

Acetamides↗

Cyanide removal by Chinese vegetation--quantification of the Michaelis-Menten kinetics.

BACKGROUND: Little is known about metabolism rates of environmental chemicals by vegetation. A good model compound to study the variation of rates among plant species is cyanide. Vascular plants possess an enzyme system that detoxifies cyanide by converting it to the amino acid asparagine. Knowledge of the kinetic parameters, the half-saturation constant (Km) and the maximum metabolic capacity (vmax), is very useful for enzyme characterization and biochemical purposes. The goal of this study is to find the enzyme kinetics (K(M) and vmax) during cyanide metabolism in the presence of Chinese vegetation, to provide quantitative data for engineered phytoremediation, and to investigate the variation of metabolic rates of plants. METHODS: Detached leaves (1.0 g fresh weight) from 12 species out of 9 families were kept in glass vessels with 100 mL of aqueous solution spiked with potassium cyanide at 23 degrees C for 28 h. Four different treatment concentrations of cyanide were used, ranging from 0.44 to 7.69 mg CN/L. The disappearance of cyanide from the aqueous solution was analyzed spectrophotometrically. Realistic values of the half-saturation constant (KM) and the maximum metabolic capacity (vmax) were estimated by a computer program using non-linear regression treatments. As a comparison, Lineweaver-Burk plots were also used to estimate the kinetic parameters. RESULTS AND DISCUSSION: The values obtained for K(M) and vmax varied with plant species. Using non-linear regression treatments, values of vmax and K(M) were found in a range between 6.68 and 21.91 mg CN/kg/h and 0.90 to 3.15 mg CN/L, respectively. The highest vmax was by Chinese elder (Sambucus chinensis), followed by upright hedge-parsley (Torilis japonica). The lowest Vmax was demonstrated by the hybrid willow (Salix matssudana x alba). However, the highest K(M) was found in the water lily (Nymphea teragona), followed by the poplar (Populus deltoides Marsh). The lowest K(M) was demonstrated by corn (Zea mays L.). The values of vmax were normally distributed with a mean of 13 mg CN/kg/h. CONCLUSIONS: Significant removal of cyanide from aqueous solution was observed in the presence of plant materials without phytotoxicity, even at high doses of cyanide. This gives rise to the conclusion that the Chinese plant species used in this study are all able to efficiently metabolize cyanide, although with different maximum metabolic capacities. A second conclusion is that the variation of metabolism rates between species is small. All these plants had a similar K(M), indicating the same enzyme is active in all plants. RECOMMENDATIONS AND OUTLOOK: Detoxification of cyanide with trees seems to be a feasible option for cleaning soils and water contaminated with cyanide. For phytoremediation projects, screening appropriate plant species adapted to local conditions should be seriously considered. More chemicals should be investigated to find common principles of the metabolism of environmental chemicals by plants.

Biodegradation, Environmental↗