Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol

The haloalkane dehalogenase LinB from Sphingobium indicum B90A converts β-hexachlorocyclohexane (β-HCH), the most persistent HCH stereoisomer, to mono- and dihydroxylated metabolites. Recently, we reported that LinB also transforms α-, β- and γ-hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. Here, we show that LinB catalyzes the hydroxylation of δ-HBCD to two pentabromocyclododecanols (PBCDOHs) and two tetrabromocyclododecadiols (TBCDDOHs). The stereochemistry of this enzymatic transformation was deduced from XRD crystal structure data of the substrate δ-HBCD and α₂-PBCDOH, one of the biotransformation products. Five stereocenters of δ-HBCD are unchanged but the one at C6 is converted to an alcohol with inversion from S- to R-configuration in a nucleophilic, S_N2-like substitution reaction. Only α₂-PBCDOH with the 1R,2R,5S,6R,9R,10S-configuration is obtained but not its enantiomer. With only two of the 64 PBCDOHs formed, these transformations indeed are regio- and stereoselective. A conformational analysis revealed that the triple-turn motive, which is predominant in δ-HBCD and in several other HBCD stereoisomers, is also found in the product. This shows that LinB preferentially converted reactive bromine atoms but not those in the conserved triple-turn motive. The widespread contamination with HCHs triggered the bacterial evolution of dehalogenases which acquired the ability to convert these pollutants and their metabolites. We here demonstrate that LinB of S. indicum also transforms HBCDs regio- and stereoselectively following a similar mechanism.     

Analysis of a population of magnetotactic bacteria of the Gulf of Gabès,Tunisia

The occurrence of magnetotactic bacteria (MTB) on a Tunisian marine coast exposed to heavy metals pollution (Sfax, Gulf of Gabès, Mediterranean Sea) was investigated. The MTB population of this Southern Mediterranean coast was compared to the MTB populations previously investigated on the French Northern Mediterranean coast. A dominant MTB coccus morphotype was observed by microscopy analysis. By pyrosequencing technology, the analysis of the 16S ribosomal RNA (rDNA) revealed as much as 33 operational taxonomic sequence units (OTUs) close to sequences of MTB accessible in the databases. The majority were close to MTB sequences of the “Med group” of α-Proteobacteria. Among them, a dominant OTU_001 (99 % of the MTB sequences) affiliated within the Magnetococcales order was highlighted. Investigating the capacities of this novel bacterium to be used in bioremediation and/or depollution processes could be envisaged.     

Effects of conditioning,cross‐conditioning,and microbial growth on development of enhanced biodegradation of insecticides in soil

Abstract

Pretreatment of a Drummer‐Catlin soil mixture with granular formulations of carbofuran or trimethacarb enhanced biodegradation of subsequent treatments with the technical formulations. Degradation of carbofuran was enhanced by pretreatments with trimethacarb, and degradation of trimethacarb was enhanced by pretreatments with carbofuran. Bendiocarb degradation was enhanced by pretreatments of soil with carbofuran or trimethacarb. In bioassays with southern corn rootworm larvae, biological activity of carbofuran, trimethacarb, and bendiocarb was rapidly lost in soils pretreated with granular formulations. Pretreatment of soil with granular terbufos did not enhance the biodegradation of subsequent applications of technical terbufos. Several microbial biomass assays showed an increase in specific carbofuran‐degrading bacteria in soils that were pretreated with carbofuran. Bacteria were isolated that could grow on carbofuran and apparently degrade it when present with another carbon source.     

A multivariate statistical analysis of the composition of rainwater near Cubatão, SP, Brazil

With the aim of estimating the chemical composition of bulk precipitation (wet + dry) in Cubat?o, rainwater samples were collected at several localities in the Cubat?o region from May 1984 to October 1985. The levels of some inorganic ions (Na+, Ca2+, K+, Mg2+, Cl-, SO4(2-), NH4+, PO4(3-)) were measured by atomic absorption spectrophotometry, turbidimetry and titration analysis. Correlation and Fisher discrimination indices, principal component and varimax loading and scores were determined in the multivariate statistical data treatment. The results showed that ionic concentrations in rainwater from Vila Parisi are significantly higher than those of Cubat?o Centro, Santos and Serra do Mar. The ionic compositions of the Vila Parisi rainwater seem to be mainly determined by local anthropogenic activities (industrial pollution). Besides the influence of this factor on water quality, there is also a natural oceanic contribution involving Cl- and Na+ at the other locations.     

Economic,ecological, and health aspects of β-diketonate application in the process of water purification

Environmental Science and Pollution Research - Water pollution is a constant challenge for humanity. Sustainable economic development and environmental protection through a green economy structure...     

Vertical and horizontal distribution,source identification,ecological and toxic risk assessment of heavy metals in sediments of Lake Aygır,Kars, Turkey

Surface and core sediment samples were collected from Lake Ayg?r, Turkey, to determine heavy metal distribution, probable sources and potential ecological and toxic risks for the lake. Heavy metals, total sulfur, total phosphate, total organic carbon, chlorophyll degradation products, and CaCO₃ content were established. The enrichment factor, PLI, potential ecological risk index, and toxic risk index were calculated. Zn was determined to have the highest accumulation in surface sediment, followed by Cr, Pb, and Cd, respectively. Cd was the only element that exceeded the critical value of 40 and posed a moderate potential ecological risk. According to TRI, no ecotoxic risk was found. It is thought that local fossil fuel consumption is responsible for the accumulation of heavy metals since there is a lack of urbanization, industrialization, and agricultural activities around the lake.     

Toxicity, dioxin-like activities, and endocrine effects of DDT metabolites—DDA, DDMU, DDMS, and DDCN

Background, aim, and scope  

2,2-bis(chlorophenyl)-1,1,1-trichloroethane (DDT) metabolites, other than those routinely measured [i.e., 2,2-bis(chlorophenyl)-1,1-dichloroethylene (DDE) and 2,2-bis(chlorophenyl)-1,1-dichloroethane (DDD)], have recently been detected in elevated concentrations not only in the surface water of Teltow Canal, Berlin, but also in sediment samples from Elbe tributaries (e.g., Mulde and Havel/Spree). This was paralleled by recent reports that multiple other metabolites could emerge from the degradation of parent DDT by naturally occurring organisms or by interaction with some heavy metals. Nevertheless, only very few data on the biological activities of these metabolites are available to date. The objective of this communication is to evaluate, for the first time, the cytotoxicity, dioxin-like activity, and estrogenicity of the least-studied DDT metabolites.     

Comparative acute toxicity of leachates from plastic products made of polypropylene, polyethylene, PVC, acrylonitrile–butadiene–styrene, and epoxy to Daphnia magna

Purpose

The large global production of plastics and their presence everywhere in the society and the environment create a need for assessing chemical hazards and risks associated with plastic products. The aims of this study were to determine and compare the toxicity of leachates from plastic products made of five plastics types and to identify the class of compounds that is causing the toxicity.

Methods

Selected plastic types were those with the largest global annual production, that is, polypropylene, polyethylene, and polyvinyl chloride (PVC), or those composed of hazardous monomers (e.g., PVC, acrylonitrile?Cbutadiene?Cstyrene [ABS], and epoxy). Altogether 26 plastic products were leached in deionized water (3?days at 50°C), and the water phases were tested for acute toxicity to Daphnia magna. Initial Toxicity Identification Evaluations (C18 filtration and EDTA addition) were performed on six leachates.

Results

For eleven leachates (42%) 48-h EC50s (i.e the concentration that causes effect in 50 percent of the test organisms) were below the highest test concentration, 250 g plastic/L. All leachates from plasticized PVC (5/5) and epoxy (5/5) products were toxic (48-h EC50s ranging from 2 to 235?g plastic/L). None of the leachates from polypropylene (5/5), ABS (5/5), and rigid PVC (1/1) products showed toxicity, but one of the five tested HDPE leachates was toxic (48-h EC50 17?C24?g plastic/L). Toxicity Identification Evaluations indicated that mainly hydrophobic organics were causing the toxicity and that metals were the main cause for one leachate (metal release was also confirmed by chemical analysis).

Conclusions

Toxic chemicals leached even during the short-term leaching in water, mainly from plasticized PVC and epoxy products.     

Energy,food, and land — The ecological traps of humankind

Humans’ superiority over all other organisms on earth rests on five main foundations: command of fire requiring fuel; controlled production of food and other biotic substances; utilization of metals and other non-living materials for construction and appliances; technically determined, urban-oriented living standard; economically and culturally regulated societal organization. The young discipline of ecology has revealed that the progress of civilization and technology attained, and being further pursued by humankind, and generally taken for granted and permanent, is leading into ecological traps. This metaphor circumscribes ecological situations where finite resources are being exhausted or rendered non-utilizable without a realistic prospect of restitution. Energy, food and land are the principal, closely interrelated traps; but the absolutely decisive resource in question is land whose increasing scarcity is totally underrated. Land is needed for fulfilling growing food demands, for producing renewable energy in the post-fossil and post-nuclear era, for maintaining other ecosystem services, for urban-industrial uses, transport, material extraction, refuse deposition, but also for leisure, recreation, and nature conservation. All these needs compete for land, food and non-food biomass production moreover for good soils that are scarcer than ever. We are preoccupied with fighting climate change and loss of biodiversity; but these are minor problems we could adapt to, albeit painfully, and their solution will fail if we are caught in the interrelated traps of energy, food, and land scarcity. Land and soils, finite and irreproducible resources, are the key issues we have to devote our work to, based on careful ecological information, planning and design for proper uses and purposes. The article concludes with a short reflection on economy and competition as general driving forces, and on the role and reputation of today’s ecology. Updated version of the keynote lecture presented at the EcoSummit 2007 in Beijing, China, May 24. The article is gratefully dedicated to the memory of my late colleague and friend Frank B. Golley.     

Geological characterization and environmental implications of the placement of the Morelia Dump, Michoacán, Central Mexico

The landfill of Morelia, the capital city of the state of Michoacán in central-western Mexico, is located 12 km west of the city and has operated since 1997 without a structure engineered and designed to control the generation in situ of biogas and leachates. A geological evaluation of the landfill site is presented in this paper. The results indicate that the site lacks ideal impermeable subsurface strata. The subsurface strata consist of highly fractured basaltic lava flows (east-west fault and fracture system trend) and sand-size cineritic material with high permeability and porosity. Geochemical analysis of groundwater from Morelia's municipal aquifer shows a high concentration of heavy metals (Cd, Pb, As) exceeding the Mexican environmental regulations, along with the presence of some organic pollutants (phenols). Analyses of samples of the landfill's permanent leachate ponds show very high concentrations of the same contaminants. Samples were taken from the leachate pond and from nearby water-wells during the rainy season (summer 1997) and the dry season (spring 1997, 1998, and 1999). In all cases, the concentration of contaminants registered exceeded the standards for drinking water of the World Health Organization (American Public Health Association, American Water Works Association, and Water Pollution Control Federation, 2000). Some metal contaminants could be leaching directly from the landfill.     

Geological Characterization and Environmental Implications of the Placement of the Morelia Dump,Michoacán,Central Mexico

Abstract

The landfill of Morelia, the capital city of the state of Michoacán in central-western Mexico, is located 12 km west of the city and has operated since 1997 without a structure engineered and designed to control the generation in situ of biogas and leachates. A geological evaluation of the landfill site is presented in this paper. The results indicate that the site lacks ideal impermeable sub-surface strata. The subsurface strata consist of highly fractured basaltic lava flows (east-west fault and fracture system trend) and sand-size cineritic material with high permeability and porosity. Geochemical analysis of groundwater from Morelia’s municipal aquifer shows a high concentration of heavy metals (Cd, Pb, As) exceeding the Mexican environmental regulations, along with the presence of some organic pollutants (phenols). Analyses of samples of the landfill’s permanent leachate ponds show very high concentrations of the same contaminants. Samples were taken from the leachate pond and from nearby water-wells during the rainy season (summer 1997) and the dry season (spring 1997, 1998, and 1999). In all cases, the concentration of contaminants registered exceeded the standards for drinking water of the World Health Organization (American Public Health Association, American Water Works Association, and Water Pollution Control Federation, 2000). Some metal contaminants could be leaching directly from the landfill.     

Does (K+Mg+Ca+P) fertilization lead to recovery of tree health in a nitrogen stressed Quercus rubra L. stand?

In The Netherlands atmospheric deposition of nitrogen compounds to forest ecosystems has been very high for some decades and has led to severe nutritional imbalances in soils as well as in trees. At this moment legislation is not fully in effect with respect to lowering emission/deposition fluxes, particularly of nitrogen. The trees suffer mainly from severe magnesium, potassium and calcium and sometimes phosphorus deficiencies. In this study it was investigated whether fertilization with potassium, magnesium, calcium and phosphorus could prevent a Quercus rubra stand from further decline by restoring the nutritional balance, though the detrimental input of nitrogen compounds still continues. Three fertilization treatments were applied: (i) a standard dose of 1250 kg.ha(-1) containing 60 kg P.ha(-1) (as P2O5), 100 kg K.ha(-1) (as K2O), 80 kg Mg.ha(-1) (as MgO) and 340 kg Ca.ha(-1) (as CaCO3); (ii) two times the standard dose; and (iii) three times the standard dose. Soil solution chemistry showed that the highest dose led to the most significant results: an improved nutrient balance and an increased availability of nutrients. After one growing season following fertilization, the trees looked much healthier and crown density had increased. This revitalization lasted for at least four years. For tree health the mid dose seemed appropriate. After the first growing season potassium is the most mobile nutrient, in the soil and also in the trees, but tended to decrease in the fourth year after fertilization. Magnesium and calcium reached normal values in the leaves after four growing seasons. No obvious effects of phosphorus were found.     

Distribution,persistence, and fate of mexacarbate in the aquatic environment of a mixed‐wood boreal forest

Abstract

The distribution and persistence of aerially applied mexacarbate were studied in a New Brunswick aquatic forest environment after spraying twice at a dosage of 70 g A.l./ha using a fixed‐wing aircraft. Average droplet density (drops/cm²) and ground deposition (g A.1./ha) between the two applications differed considerably. The values for the first and second applications were 1.7 and 0.73, and 5.2 and 2.0, respectively; but the average NMD (20 μm) and VMD (36 μm) for both applications were nearly the same. The maximum 1‐h postspray concentrations of mexacarbate in the stream and pond waters were 0.73 and 18.74 ppb, respectively. Concentrations fell rapidly to below detection limits within 12 h in stream and within 3 d in pond water. Cattails (Typha latifolia), manna grass (Glyceria borealis) and bog moss (Sphagnum sp.) collected from the pond contained peak 1‐h postspray concentrations of 720, 482 and 81 ppb, respectively. The concentration levels decreased rapidly and the average half‐lives of the chemical in them were about 3.9, 8.5 and 2.0 h. Bog moss, stream moss (Fontinalis sp.), watercress (Nasturtium officinalis), buttercup (Ranunculus aquatilis) and green alga (Drapamaldia sp.) sampled from the stream sites did not contain measurable levels of mexacarbate. Also, caged and wild tadpoles (Rana clamitans melanota) from the pond, and brook trout (Salvelinus fontinalis) (caged and wild), Atlantic salmon (Salmo salar) (wild) and mayfly nymphs (Ephemeralla sp.) collected from the stream did not contain any of the material. Mexacarbate was not detected in stream and pond sediments. The demethylated products, 4‐methylamino and 4‐amino‐3,5‐xylyl methylcarbamates and the phenol, 4‐dimethylamino‐3,5‐xylenol, were frequently detected as metabolites in water and in the aquatic plants. The presence of these compounds showed that demethylation and hydrolytic routes are the major metabolic pathways for the dissipation of mexacarbate from these substrates.     

Comparison of nitroethane, 2-nitro-1-propanol, lauric acid, Lauricidin® and the Hawaiian marine algae, Chaetoceros, for potential broad-spectrum control of anaerobically grown lactic acid bacteria

The gastrointestinal tract of bovines often contains bacteria that contribute to disorders of the rumen, and may also contain foodborne or opportunistic human pathogens as well as bacteria capable of causing mastitis in cows. Thus there is a need to develop broad-spectrum therapies that are effective while not leading to unacceptably long antibiotic withdrawal times. The effects of the CH(4)-inhibitors nitroethane (2 mg/mL), 2-nitro-1-propanol (2 mg/mL), lauric acid (5 mg/mL), the commercial product Lauricidin? (5 mg/mL), and a finely ground product of the Hawaiian marine algae, Chaetoceros (10 mg/mL), were compared in pure cultures of Streptococcus agalactia, Enterococcus faecium, Streptococcus bovis, and in a mixed lactic acid rumen bacterial culture. Lauricidin? and lauric acid exhibited the most bactericidal acidity against all bacteria. These results suggest potential animal health benefits from supplementing cattle diets with lauric acid or Lauricidin? to improve the health of the rumen and help prevent shedding of human pathogens.     

Residues of chlorpyrifos‐methyl in balsam fir foliage,forest litter,soil, stream water,sediment and fish tissue after double aerial applications of Reldan®

Abstract

Chlorpyrifos‐methyl was applied twice at 70 g A.I./ha by means of a fixed‐wing aircraft to a mixed coniferous forest near Allardville, New Brunswick. Residue in balsam fir foliage was highest (1 ppm wet wt) 1 hr after spraying and rapidly declined to about 30% within 1 day, but persisted at a very low level (0.03 ppm wet wt) for 125 days. Current year's foliage contained a higher level of residue than old foliage. Chlorpyrifos‐methyl persisted longer in forest litter than in soil. After 125 days, trace amounts (< 6 ppb wet wt) were still found in litter but were not detected in soil. In stream water the residue dissipated very rapidly; more than 90% disappeared 3 hours after the second application and were not detected after 4 days. Low‐level residue (< 0.1 ppm wet wt) was present in the sediment and persisted for 10 days. Although brook trout and slimy sculpin captured in the stream within 3 days of the second application contained residues (< 0.05 ppm fresh wt) none were detected in any fish captured, 9 and 47 days later.     

Evaluation of mutagenic potential of contaminated atmosphere at Ibirapuera Park, São Paulo - SP, Brazil, using the Tradescantia stamen-hair assay

We report seasonal variation in CH(4) and N(2)O emission rate from solid storage of bovine manure in Delhi as well as emission factors and emission inventory from manure management systems in India. Emission flux observed in the year 2002-2003 was 4.29+/-1, 4.84+/-2.44 and 12.92+/-4.25 mg CH(4)kg(-1)dung day(-1), as well as 31.29+/-4.93, 72.11+/-16.22 and 6.39+/-1.76 microgN(2)O kg(-1)dung day(-1) in winter, summer and rainy seasons, respectively. CH(4) emission factors varied from 0.8 to 3.3 kg hd(-1)year(-1) for bovines and were lower than IPCC-1996 default values. N(2)O emission factors varied from 3 to 11.7 mg hd(-1)year(-1) from solid storage of manure. Inventory estimates were found to about 698+/-27 Gg CH(4) from all manure management systems and 2.3+/-0.46 tons of N(2)O from solid storage of manure for the year 2000.     

Increased Bioavailability of Mercury in the Lagoons of Lomé, Togo: The Possible Role of Dredging

Surface sediments of the lagoons of Lomé, Togo, were analyzed for mercury, methylmercury, and trace elements. Concentrations were greater than typical for natural lagoon sediments, and with greater variability within the Eastern lagoon compared to the Western one. The Eastern lagoon is larger and has been dredged in the past, while the Western lagoon, which also receives major waste inputs, has not been dredged and shows less tidal flushing. Accordingly, one naturally believes that the Eastern lagoon is cleaner and probably safe to use due to its natural resources, including fishes to eat. Unexpectedly, we describe here that mercury methylation was greater in the Eastern lagoon, indicating increased bioavailability of mercury, as probably facilitated by past dredging that decreased solid-phase retention of inorganic mercury. Urbanization has historically been more developed in the southern part of the lagoons, which is still reflected in contamination levels of sediment despite dredging, probably because sources of contamination are still more important there today. Such urban contamination emphasizes the need to regulate waste discharges and possible airborne contamination in growing cities of developing countries, and implements environmental and public health monitoring, especially in relation to misbelieves systematically associated with the cleansing effect of dredging activity.     

Crystal structure of δ-isobutoxypentabromo-cyclododecanes, kinetics and selectivity of their isomerization during thermal treatment of flame-proofed polystyrenes

Hexabromocyclododecanes (HBCDs) are persistent organic pollutants now ubiquitous in the environment. Technical HBCD mixtures and with it flame-proofed polystyrenes (FP-PS) also contain isobutoxypentabromocyclododecanes (iBPBCDs) as minor constituents, which are possibly released together with HBCDs. So far, eight diastereomeric pairs of enantiomers named as α-, β-, γ-, δ-, ?-, ξ-, η-, and θ-iBPBCDs with proportions of 10%, 5%, 2%, 21%, 11%, 11%, 12% and 28% were found in technical HBCD. Herein the crystal structure of racemic δ-iBPBCD, the second most prominent diastereomer, is presented and assigned to (1S)-1-isobutoxy-(2R,5R,6S,9S,10S)-2,5,6,9,10-pentabromocyclododecane and its enantiomer. During thermal treatment of FP-PS, e.g. the production of extruded polystyrenes (XPS), proportions of δ-iBPBCDs decrease and those of other stereoisomers increase. Evidence was found that δ-iBPBCDs isomerize stereo- and regioselectively to β-iBPBCDs. Based on structural and kinetic data, a transformation mechanism was proposed. Apparent first-order rate constants (k_iso) of 0.0019, 0.0050, and 0.012 min⁻¹ are found for the δ- to β-iBPBCD isomerization at 120, 130, and 140 °C, respectively, corresponding to half-lives of 360, 140, and 56 min. These transformations also occur during the production of XPS, which predominantly contain β-iBPBCDs, whereas δ-iBPBCDs dominate in materials experiencing lower thermal stress, e.g. expanded polystyrenes (EPS). The relative configurations of δ- and θ-iBPBCDs are TtCtCt, like the one of γ-HBCDs. γ-HBCDs are the kinetically and α-HBCDs with a TcCtCc configuration the thermodynamically favored products. In analogy, β-iBPBCDs are assumed to have a TcCtCc configuration like α-HBCDs because they are formed from δ-iBPBCDs under thermodynamic control. In conclusion, HBCD- and iBPBCD-patterns in flame-proofed polystyrenes vary substantially, reflecting the thermal stress these materials have experienced. When released to the environment, these patterns might further change, as observed for HBCDs.     

The use of vegetation,bees, and snails as important tools for the biomonitoring of atmospheric pollution—a review

The continuous discharge of diverse chemical products in the environment is nowadays of great concern to the whole world as some of them persist in the environment leading to serious diseases. Several sampling techniques have been used for the characterization of this chemical pollution, although biomonitoring using natural samplers has recently become the technique of choice in this field due to its efficiency, specificity, and low cost. In fact, several living organisms known as biomonitors could accumulate the well-known persistent environmental pollutants allowing their monitoring in the environment. In this work, a review on environmental biomonitoring is presented. The main sampling techniques used for monitoring environmental pollutants are first reported, followed by an overview on well-known natural species used as passive samplers and known as biomonitors. These species include conifer needles, lichen, mosses, bees and their byproducts, and snails, and were widely used in recent research as reliable monitors for environmental pollution.