Toxicity of fenamiphos and its metabolites to the cladoceran Daphnia carinata: the influence of microbial degradation in natural waters

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide, fenamiphos sulfone, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, to a cladoceran, Daphnia carinata was studied in both cladoceran culture medium and natural water collected from a local river. The toxicity followed the order: fenamiphos>fenamiphos sulfone>fenamiphos sulfoxide. The hydrolysis products of fenamiphos, F. sulfoxide (FSO) and F. sulfone (FSO(2)) (F. phenol, FSO phenol and FSO(2) phenol) were not toxic to D. carinata up to 500microgl(-1) water, suggesting hydrolysis reaction leads to detoxification. Also the toxicity was reduced in natural water compared to the cladoceran culture medium due to microbial mediated degradation of toxicants in the natural water. Fenamiphos and its metabolites were stable in both cladoceran water and filter-sterilised natural water while these compounds showed degradation in unfiltered natural water implicating the microbial role in degradation of these compounds. To our knowledge this is the first study on acute toxicity of fenamiphos metabolites to cladoceran and this study suggests that the organophosphate pesticides are highly toxic to fresh water invertebrates and therefore pollution with these compounds may adversely affect the natural ecosystems.     

The use of molecular techniques to characterize the microbial communities in contaminated soil and water

Traditionally, the identification and characterization of microbial communities in contaminated soil and water has previously been limited to those microorganisms that are culturable. The application of molecular techniques to study microbial populations at contaminated sites without the need for culturing has led to the discovery of unique and previously unrecognized microorganisms as well as complex microbial diversity in contaminated soil and water which shows an exciting opportunity for bioremediation strategies. Nucleic acid extraction from contaminated sites and their subsequent amplification by polymerase chain reaction (PCR) has proved extremely useful in assessing the changes in microbial community structure by several microbial community profiling techniques. This review examines the current application of molecular techniques for the characterization of microbial communities in contaminated soil and water. Techniques that identify and quantify microbial population and catabolic genes involved in biodegradation are examined. In addition, methods that directly link microbial phylogeny to its ecological function at contaminated sites as well as high throughput methods for complex microbial community studies are discussed.     

Integration of traditional and innovative characterization techniques for flux-based assessment of Dense Non-aqueous Phase Liquid (DNAPL) sites

Key attributes of the source zone and the expanding dissolved plume at a trichloroethene (TCE) site in Australia were evaluated using trends in groundwater monitoring data along with data from on-line volatile organic compound (VOC) samplers and passive flux meters (PFMs) deployed in selected wells. These data indicate that: (1) residual TCE source mass in the saturated zone, estimated using two innovative techniques, is small ( 10 kg), which is also reflected in small source mass discharge ( 3 g/day); (2) the plume is disconnecting, based on TCE concentration contours and TCE fluxes in wells along a longitudinal transect; (3) there is minimal biodegradation, based on TCE mass discharge of  6 g/day at a plume control plane  175 m from source, which is also consistent with aerobic geochemical conditions observed in the plume; and (4) residual TCE in the vadose zone provides episodic inputs of TCE mass to the plume during infiltration/recharge events. TCE flux data also suggest that the small residual TCE source mass is present in the low-permeability zones, thus making source treatment difficult. Our analysis, based on a synthesis of the archived data and new data, suggests that source treatment is unwarranted, and that containment of the large TCE plume ( 1.2 km long,  0.3 km wide; 17 m deep;  2000–2500 kg TCE mass) or institutional controls, along with a long-term flux monitoring program, might be necessary. The flux-based site management approach outlined in this paper provides a novel way of looking beyond the complexities of groundwater contamination in heterogeneous domains, to make intelligent and informed site decisions based on strategic measurement of the appropriate metrics.     

Heterogeneous Fenton oxidation of Direct Black G in dye effluent using functional kaolin-supported nanoscale zero iron

This study investigated kaolin-supported nanoscale zero-valent iron (nZVI/K) as a heterogeneous Fenton-like catalyst for the adsorption and oxidation of an azo dye, Direct Black G (DBG). New findings suggest that kaolin as a support material not only reduced the aggregation of nanoscale zero-valent iron (nZVI) but also improved the adsorption of DBG. It consequently improved Fenton oxidation by increasing the local concentration of DBG in the vicinity of nZVI. This was confirmed by scanning electron microscopy and X-ray diffraction for the surface morphology of nZVI/K before and after the Fenton-like reaction. Furthermore, nZVI/K proved to be a catalyst for the heterogeneous Fenton-like oxidation of the DBG process in the neutral pH range. More than 87.22 % of DBG was degraded, and 54.60 % of total organic carbon was removed in the optimal conditions: 0.6 g/L dosage of nZVI/K, 33 mM H₂O₂, 100 mg/L initial DBG concentration, temperature of 303 K and pH of 7.06. Finally, it was demonstrated that nZVI/K removed DBG from dye wastewater through the processes of adsorption and oxidation.     

Remediation of metalliferous mines,revegetation challenges and emerging prospects in semi-arid and arid conditions

Understanding plant behaviour in polluted soils is critical for the sustainable remediation of metal-polluted sites including abandoned mines. Post-operational and abandoned metal mines particularly in semi-arid and arid zones are one of the major sources of pollution by soil erosion or plant hyperaccumulation bringing ecological impacts. We have selected from the literature 157 species belonging to 50 families to present a global overview of ‘plants under action’ against heavy metal pollution. Generally, all species of plants that are drought, salt and metal tolerant are candidates of interest to deal with harsh environmental conditions, particularly at semi-arid and arid mine sites. Pioneer metallophytes namely Atriplex nummularia, Atriplex semibaccata, Salsola kali, Phragmites australis and Medicago sativa, representing the taxonomic orders Caryophyllales, Poales and Fabales are evaluated in terms of phytoremediation in this review. Phytoremediation processes, microbial and algal bioremediation, the use and implication of tissue culture and biotechnology are critically examined. Overall, an integration of available remediation plant-based technologies, referred to here as ‘integrated remediation technology,’ is proposed to be one of the possible ways ahead to effectively address problems of toxic heavy metal pollution.

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Graphical abstract Integrated remediation technology (IRT) in metal-contaminated semi-arid and arid conditions. The hexagonal red line represents an IRT concept based on remediation decisions by combination of plants and microbial processes.

     

Atrazine and simazine degradation in Pennisetum rhizosphere

The ability of rhizosphere of four plant species to promote the degradation of charcoal-fixed atrazine and simazine in cement blocks of a long-term contaminated soil when mixed with a normal soil at 1:1 ratio was tested. Of the four selected plants viz., rye grass (Lolium perenne), tall fescue (Festuca arundinacae), Pennisetum (Pennisetum clandestinum) and a spring onion (Allium sp.) used in this study, only P. clandestinum was able to survive in herbicide contaminated soil while other plants died within few days after germination/transplanting. Both atrazine and simazine were degraded at a faster rate in contaminated soil planted to P. clandestinum than in unplanted soil. Within 80 days, nearly 45% and 52% of atrazine and simazine, respectively, were degraded in soil planted to P. clandestinum while only 22% and 20% of the respective herbicide were degraded in the unplanted soil. During 80-day experimental period, both microbial biomass and soil dehydrogenase activity were significantly increased (7-fold) in soil planted to P. clandestinum over that in unplanted soil. The suspension of contaminated rhizosphere soil, planted to P. clandestinum exhibited an exceptional capability to degrade both atrazine (300 microg) and simazine (50 microg) in a mineral salts medium over that of non-rhizosphere soil suspension. Results indicate that P. clandestinum, a C4 plant, may be useful for remediation of soils contaminated with atrazine and simazine.     

Degradation of fenamiphos in soils collected from different geographical regions: The influence of soil properties and climatic conditions

The persistence of fenamiphos (nematicide) in five soils collected from different geographical regions such as Australia, Ecuador and India under three temperature regimes (18, 25 and 37°C) simulating typical environmental conditions was studied. The effect of soil properties (soil pH, temperature and microbial biomass) on the degradation of fenamiphos was determined. The rate of degradation increased with increase in temperature. Fenamiphos degradation was higher at 37°C than at 25 and 18°C (except under alkaline pH). The degradation pathway differed in different soils. Fenamiphos sulfoxide (FSO) was identified as the major degradation product in all the soils. Fenamiphos sulfone (FSO₂), and the corresponding phenols: fenamiphos phenol (FP), fenamiphos sulfoxide phenol (FSOP) and fenamiphos sulfone phenol (FSO₂P) were also detected. The degradation of fenamiphos was faster in the alkaline soils, followed by neutral and acidic soils. Under sterile conditions, the dissipation of the pesticide was slower than in the non-sterile soils suggesting microbial role in the pesticide degradation. The generation of new knowledge on fenamiphos degradation patterns under different environmental conditions is important to achieve better pesticide risk management.     

The influence of biochar and black carbon on reduction and bioavailability of chromate in soils

The widespread use of chromium (Cr) has a deleterious impact on the environment. A number of pathways, both biotic and abiotic in character, determine the fate and speciation of Cr in soils. Chromium exists in two predominant species in the environment: trivalent [(Cr(III)] and hexavalent [Cr(VI)]. Of these two forms, Cr(III) is nontoxic and is strongly bound to soil particles, whereas Cr(VI) is more toxic and soluble and readily leaches into groundwater. The toxicity of Cr(VI) can be mitigated by reducing it to Cr(III) species. The objective of this study was to examine the effect of organic carbon sources on the reduction, microbial respiration, and phytoavailability of Cr(VI) in soils. Organic carbon sources, such as black carbon (BC) and biochar, were tested for their potential in reducing Cr(VI) in acidic and alkaline contaminated soils. An alkaline soil was selected to monitor the phytotoxicity of Cr(VI) in sunflower plant. Our results showed that using BC resulted in greater reduction of Cr(VI) in soils compared with biochar. This is attributed to the differences in dissolved organic carbon and functional groups that provide electrons for the reduction of Cr(VI). When increasing levels of Cr were added to soils, both microbial respiration and plant growth decreased. The application of BC was more effective than biochar in increasing the microbial population and in mitigating the phytotoxicity of Cr(VI). The net benefit of BC emerged as an increase in plant biomass and a decrease in Cr concentration in plant tissue. Consequently, it was concluded that BC is a potential reducing amendment in mitigating Cr(VI) toxicity in soil and plants.     

Bioavailability and toxicity of cadmium to microorganisms and their activities in soil: a review

Significant quantities of cadmium (Cd) have been added to the soils globally due to various anthropogenic activities, raising concerns for environmental health. Microorganisms play a unique role in the soil ecosystem, because of their contributions to soil fertility. Contrasting trends, reported on the toxic effects of heavy metals including Cd on soil microorganisms and their activities, are attributable to short-term studies often limited to a single soil type and conducted under controlled laboratory conditions. There is a paucity of reliable field data on Cd alone, since most field studies on Cd-microorganism interactions in soils are based on sewage sludge containing multimetals and organic substances. No single parameter can be used to generalize Cd toxicity and different parameters can provide contrasting results. A battery of relevant tests, rather than just one single assay, involving important microbial activities should therefore be included in ecotoxicity studies. The bioavailability of Cd and associated toxicity to soil biota vary with time, soil type, speciation, ageing, Cd-source, organisms and the environmental factors. The available fraction or soil solution Cd, and not the total concentration of Cd, seems to correlate well with the toxicity parameters.     

Effects of long-term contamination of DDT on soil microflora with special reference to soil algae and algal transformation of DDT

DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane) and its principle metabolites, DDE (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene) and DDD (1,1-dichloro-2,2-bis(p-chlorophenyl)ethane) are widespread environmental contaminants but little information is available concerning their effects on non-target microflora (especially microalgae and cyanobacteria) and their activities in long-term contaminated soils. For this reason a long-term DDT-contaminated soil was screened for DDT residues and toxicity to microorganisms (bacteria, fungi, algae), microbial biomass and dehydrogenase activity. Also, five pure cultures isolated from various sites (two unicellular green algae and three dinitrogen-fixing cyanobacteria) were tested for their ability to metabolise DDT. Viable counts of bacteria and algae declined with increasing DDT contamination while fungal counts, microbial biomass and dehydrogenase activity increased in medium-level contaminated soil (27 mg DDT residues kg(-1) soil). All the tested parameters were greatly inhibited in high-level contaminated soil (34 mg DDT residues kg(-1) soil). Species composition of algae and cyanobacteria was altered in contaminated soils and sensitive species were eliminated in the medium and high contaminated soils suggesting that these organisms could be useful as bioindicators of pollution. Microbial biomass and dehydrogenase activity may not serve as good bioindicators of pollution since these parameters were potentially influenced by the increase in fungal (probably DDT resistant) counts. All the tested algal species metabolised DDT to DDE and DDD; however, transformation to DDD was more significant in the case of dinitrogen-fixing cyanobacteria.