Self-inhibition can limit biologically enhanced TCE dissolution from a TCE DNAPL

Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3-6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19-55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3-2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity.     

Lead tolerance and physiological adaptation mechanism in roots of accumulating and non-accumulating ecotypes of Sedum alfredii

Background, aim and scope

Lead (Pb) accumulation in soils affects plants primarily through their root systems. The aim of this study was to investigate early symptoms of the loss of membrane integrity and lipid peroxidation in root tissues and physiological adaptation mechanism to Pb in accumulating ecotypes (AE) and non-accumulating ecotypes (NAE) of Sedum alfredii under Pb stress in hydroponics.

Methods and results

Histochemical in situ analyses, fluorescence imaging, and normal physiological analysis were used in this study. Pb accumulation in roots of both AE and NAE increased linearly with increasing Pb levels (0?C200???M), and a significant difference between both ecotypes was noted. Both loss of plasma membrane integrity and lipid peroxidation in root tissues became serious with increasing Pb levels, maximum tolerable Pb level was 25 and 100???M for NAE and AE, respectively. Pb supplied at a toxic level caused a burst of reactive oxygen species (ROS) in root cells in both ecotypes. However, the root cells of AE had inherently higher activities of superoxide dismutase (SOD), guaiacol peroxidase (POD), and lipoxygenase (LOX) in control plants, and the induction response of these antioxidant enzymes occurred at lower Pb level in AE than NAE. AE plants maintained higher ascorbic acid and H₂O₂ concentrations in root cells than NAE when exposed to different Pb levels, and Pb induced more increase in dehydroascorbate (DHA), catalase (CAT), and ascorbate peroxidase (APX) in AE than NAE roots.

Discussion and conclusion

Results indicate that histochemical in situ analyses of root cell death and lipid peroxidation under Pb short-term stress was sensitive, reliable, and fast. Higher tolerance in roots of accumulating ecotype under Pb stress did depend on effective free oxygen scavenging by making complex function of both constitutively higher activities and sensitive induction of key antioxidant enzymes in root cells of S. alfredii.     

Residential runoff as a source of pyrethroid pesticides to urban creeks

Pyrethroid pesticides occur in urban creek sediments at concentrations acutely toxic to sensitive aquatic life. To better understand the source of these residues, runoff from residential neighborhoods around Sacramento, California was monitored over the course of a year. Pyrethroids were present in every sample. Bifenthrin, found at up to 73 ng/L in the water and 1211 ng/g on suspended sediment, was the pyrethroid of greatest toxicological concern, with cypermethrin and cyfluthrin of secondary concern. The bifenthrin could have originated either from use by consumers or professional pest controllers, though the seasonal pattern of discharge from the drain was more consistent with professional use as the dominant source. Stormwater runoff was more important than dry season irrigation runoff in transporting pyrethroids to urban creeks. A single intense storm was capable of discharging as much bifenthrin to an urban creek in 3 h as that discharged over 6 months of irrigation runoff.     

Satellite derived trends in NO2 over the major global hotspot regions during the past decade and their inter-comparison

We assessed satellite derived tropospheric NO₂ distribution on a global scale and identified the major NO₂ hotspot regions. Combined GOME and SCIAMACHY measurements for the period 1996-2006 have been used to compute the trends over these regions. Our analysis shows that tropospheric NO₂ column amounts have increased over the newly and rapidly developing regions like China (11 ± 2.6%/year), south Asia (1.76 ± 1.1%/year), Middle East (2.3 ± 1%/year) and South Africa (2.4 ± 2.2%/year). Tropospheric NO₂ column amounts show some decrease over the eastern US (−2 ± 1.5%/year) and Europe (0.9 ± 2.1%/year). We found that although tropospheric NO₂ column amounts decreased over the major developed regions in the past decade, the present tropospheric NO₂ column amounts over these regions are still significantly higher than those observed over newly and rapidly developing regions (except China). Tropospheric NO₂ column amounts show some decrease over South America and Central Africa, which are major biomass burning regions in the Southern Hemisphere.     

Predicting bioremediation of hydrocarbons: Laboratory to field scale

There are strong drivers to increasingly adopt bioremediation as an effective technique for risk reduction of hydrocarbon impacted soils. Researchers often rely solely on chemical data to assess bioremediation efficiently, without making use of the numerous biological techniques for assessing microbial performance. Where used, laboratory experiments must be effectively extrapolated to the field scale. The aim of this research was to test laboratory derived data and move to the field scale. In this research, the remediation of over thirty hydrocarbon sites was studied in the laboratory using a range of analytical techniques. At elevated concentrations, the rate of degradation was best described by respiration and the total hydrocarbon concentration in soil. The number of bacterial degraders and heterotrophs as well as quantification of the bioavailable fraction allowed an estimation of how bioremediation would progress. The response of microbial biosensors proved a useful predictor of bioremediation in the absence of other microbial data. Field-scale trials on average took three times as long to reach the same endpoint as the laboratory trial. It is essential that practitioners justify the nature and frequency of sampling when managing remediation projects and estimations can be made using laboratory derived data. The value of bioremediation will be realised when those that practice the technology can offer transparent lines of evidence to explain their decisions.     

In situ assays with tropical cladocerans to evaluate edge-of-field pesticide runoff toxicity

Tropical regions’ economy is usually based on agriculture, which involves an intensive use, and even frequent overuse, of pesticides. Nevertheless, not much research has been done on the impact of pesticides on tropical aquatic ecosystems, which are often contaminated by runoff-related pesticide inputs due to unpredictable and torrential rainfalls. This study aimed to: (i) adapt and evaluate a short-term sublethal in situ assay using post-exposure feeding as an endpoint, to the tropical cladoceran species Diaphanosoma brachyurum (collected at the Pedra do Cavalo dam in the Paraguaçu River basin, Bahia, Brazil), and, (ii) assess the role of the standard species Daphnia magna as an adequate laboratory surrogate. Lethal and sublethal (post-exposure feeding) responses were assessed for the two species. To evaluate these responses under environmentally realistic exposure conditions, a runoff event was simulated in an agricultural area previously contaminated with different deltamethrin concentrations. The resultant runoff water was used to set up microcosms with different dilutions, simulating the entrance of runoff water in an adjacent lentic system. An in situ assay with D. brachyurum was performed inside the microcosms, allowing to discriminate the effects due to deltamethrin from those due to other potential stressors associated with the experimental design (e.g. organism handling, load of suspended particles, microcosm design). Water samples were collected from microcosms to conduct a laboratory assay with D. magna. The in situ methodologies revealed to be suitable to conduct assays with D. brachyurum under tropical conditions, since all exposed organisms were successfully retrieved from the chambers. Furthermore, none of the potential stressors associated with the experimental design influenced the daphnids’ performance. The tropical cladoceran species, exposed under more realistic conditions, revealed to be more sensitive than the laboratory standard species: lethal effects were only observed for D. brachyurum and sublethal effects were noticed at a lower deltamethrin concentration for this species than for D. magna.     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

Heavy metals in untreated/treated urban effluent and sludge from a biological wastewater treatment plant

Background, Aim and Scope

The presence of heavy metals in wastewater is one of the main causes of water and soil pollution. The aim of the present study was to investigate the removal of Cd, Cu, Pb, Hg, Mn, Cr and Zn in urban effluent by a biological wastewater treatment, as well as to quantify the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, Tl, V and Zn in dewatering sludge from the Biological Wastewater Treatment Plant to Ribeirão Preto (RP-BWTP), Brazil.

Materials and Methods

Concentrations of Cd, Cr, Cu, Mn and Pb in wastewater and those of Ni in sludge were determined by atomic absorption spectrophotometry with graphite furnace atomization. Mercury concentrations in wastewater were measured by hydride generation atomic spectrophotometry, and Zn levels were determined by atomic absorption spectrophotometry using acetylene flame. In sludge, the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Sn, Tl, V and Zn were determined by inductively coupled plasma-mass spectrometry.

Results

The percentages of removal efficiency (RE) were the following: Hg 61.5%, Cd 60.0%, Zn 44.9%, Cu 44.2%, PB 39.7%, Cr 16,5% and Mn 10.4%. In turn, the mean concentrations (mg/kg) of metals in dewatering sludge followed this increasing order: Tl (<0.03), Hg (0.31), Be (0.43), As (1.14), Cd (1.34), V (59.2), Pb (132.1), Sn (166.1), Cr (195.0), Mn (208.1), Ni (239.4), Cu (391.7), Zn (864.4) and Fe (20537).

Discussion

The relationship between metal levels in untreated wastewater, as well as the removal efficiency are in agreement with previous data from various investigators, It is important to note that metal removal efficiency is not only affected by metal ion species and concentration, but also by other conditions such as operating parameters, physical, chemical, and biological factors.

Conclusions

Metal values recorded for treated wastewater and sludge were within the maximum permitted levels established by the Environmental Sanitation Company (CETESB), São Paulo, Brazil.

Recommendations

There is an urgent need for the authorities who are responsible for legislation on sludge uses in agriculture of establishing safety levels for As, Be, Hg, Sn, Tl and V.

Perspectives

According to the current metal levels, RP-BWTP sludge might be used for agriculture purposes. However, for an environmentally safe use of sewage sludge, further studies including systematic monitoring are recommended. Annual metal concentrations and predicted variations of those elements in the sludge should be monitored.

     

A comparison of two techniques for studying sediment desorption kinetics of hydrophobic pollutants

A comparison of two techniques (gaseous purge and vial desorption) for studying the kinetics of desorption of hydrophobic pollutants from natural sediments was conducted using identical, pre-equilibrated pollutant-sediment suspensions. Desorption profiles for the two techniques [for Lindane, Aldrin, 2,2'-dichlorobiphenyl (2,2'-DCB), 4,4'-dichlorobiphenyl (4,4'-DCB), and 2,2',6,6'-tetrachlorobiphenyl (TCB)] were then compared, based on the distribution of pollutant mass between the labile (fast) and non-labile (slow) desorption phases and the release rate constants for each phase of release. The vial desorption technique shows many practical advantages over the gaseous purge technique, including its more realistic mixing conditions, the use of an independent sample for each data point (as opposed to a calculation of a cumulative mass purged at each time point), the fact that the vials constitute a closed system and are therefore less subject to ambient contamination, and the relatively low demands of time and money for the vial technique. No consistent trends in labile rate constants or in pollutant distribution between the labile and non-labile phase were observed between the two techniques. A comparison of kinetic parameters shows much faster non-labile rate constants for the gaseous purge technique, attributed to the violent, continuous agitation employed, which likely disrupted sediment aggregates and oxidized the natural organic matter associated with the sediment. Non-labile rate constants have implications for the long-term fate of compounds adsorbed to repetitively disturbed sediments. This study suggests that the traditionally less popular vial desorption technique may yield more realistic non-labile desorption rate constants.     

Copper, zinc and cadmium in marine cage fish farm sediments: an extensive survey

The diet of cage-farmed Atlantic salmon contains a range of trace metals, some of which have toxic properties, e.g. zinc, copper and cadmium. A survey of metal concentrations (ICP-MS analysis) in surface sediments of ca. 70 stations was carried out in both May and December 2000 around a Scottish fish farm. Additionally, at 13 stations on 2 orthogonal transects centered on the farm, sediments were analysed at 1cm intervals to 8 cm depth. Maximum concentrations in surface sediments were 921, 805 and 3.5 microg g(-1) for Zn, Cu and Cd, respectively, and were found at stations near the fish farm. The calculated losses from the farm (feed input minus fish output) were 87.0%, 4.3% and 14.0% of the background-corrected inventories for Zn, Cu and Cd, respectively, indicating that for Cu and Cd at least, the feed is not the only source.