Transformation and biodegradation of 1,2,3-trichloropropane (TCP)

PURPOSE: 1,2,3-Trichloropropane (TCP) is a persistent groundwater pollutant and a suspected human carcinogen. It is also is an industrial chemical waste that has been formed in large amounts during epichlorohydrin manufacture. In view of the spread of TCP via groundwater and its toxicity, there is a need for cheap and efficient technologies for the cleanup of TCP-contaminated sites. In situ or on-site bioremediation of TCP is an option if biodegradation can be achieved and stimulated. This paper presents an overview of methods for the remediation of TCP-contaminated water with an emphasis on the possibilities of biodegradation. CONCLUSIONS: Although TCP is a xenobiotic chlorinated compound of high chemical stability, a number of abiotic and biotic conversions have been demonstrated, including abiotic oxidative conversion in the presence of a strong oxidant and reductive conversion by zero-valent zinc. Biotransformations that have been observed include reductive dechlorination, monooxygenase-mediated cometabolism, and enzymatic hydrolysis. No natural organisms are known that can use TCP as a carbon source for growth under aerobic conditions, but anaerobically TCP may serve as electron acceptor. The application of biodegradation is hindered by low degradation rates and incomplete mineralization. Protein engineering and genetic modification can be used to obtain microorganisms with enhanced TCP degradation potential.     

Particulate matter emission rates from beef cattle feedlots in Kansas-reverse dispersion modeling

Open beef cattle feedlots emit various air pollutants, including particulate matter (PM) with equivalent aerodynamic diameter of 10 microm or less (PM10); however limited research has quantified PM10 emission rates from feedlots. This research was conducted to determine emission rates of PM10 from large cattle feedlots in Kansas. Concentrations of PM10 at the downwind and upwind edges of two large cattle feedlots (KS1 and KS2) in Kansas were measured with tapered element oscillating microbalance (TEOM) PM10 monitors from January 2007 to December 2008. Weather conditions at the feedlots were also monitored. From measured PM10 concentrations and weather conditions, PM10 emission rates were determined using reverse modeling with the American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model (AERMOD). The two feedlots differed significantly in median PM10 emission flux (1.60 g/m2-day for KS1 vs. 1.10 g/m2-day for KS2) but not in PM10 emission factor (27 kg/1000 head-day for KS1 and 30 kg/1000 head-day KS2). These emission factors were smaller than published U.S. Environmental Protection Agency (EPA) emission factor for cattle feedlots.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

Distribution of PAHs and trace metals in urban stormwater sediments: combination of density fractionation,mineralogy and microanalysis

Sediment management from stormwater infiltration basins represents a real environmental and economic issue for stakeholders due to the pollution load and important tonnages of these by-products. To reduce the sediment volumes to treat, organic and metal micropollutant-bearing phases should be identified. A combination of density fractionation procedure and microanalysis techniques was used to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) within variable density fractions for three urban stormwater basin sediments. The results confirm that PAHs are found in the lightest fractions (d?d??3) whereas trace metals are equally distributed within the light, intermediary, and highest fractions (d?d?d?d?>?2.8 g cm^?3) and are mostly in the 2.3?d??3 fraction. The characterization of the five fractions by global analyses and microanalysis techniques (XRD and MEB-EDX) allowed us to identify pollutant-bearing phases. PAHs are bound to the organic matter (OM) and trace metals to OM, clays, carbonates and dense particles. Moreover, the microanalysis study underlines that OM is the main constituent responsible for the aggregation, particularly for microaggregation. In terms of sediment management, it was shown that density fractionation is not suitable for trace metals but could be adapted to separate PAH-enriched phases.     

A new bioseed for determination of wastewater biodegradability: analysis of the experimental procedure

A new bioassay proposed in the patent P201300029 was applied to a pre-treated wastewater containing a mixture of commercial pesticides to simulate a recalcitrant industrial wastewater in order to determine its biodegradability. The test uses a mixture of standardized inoculum of the lyophilized bacteria Pseudomonas putida with the proper proportion of salts and minerals. The results highlight that biodegradation efficiency can be calculated using a gross parameter (chemical oxygen demand (COD)) which facilitates the biodegradability determination for routine water biodegradability analysis. The same trend was observed throughout the assay with the dehydrated and fresh inoculums, and only a difference of 5 % in biodegradation efficiency (E _f) was observed. The obtained results showed that the P. putida biodegradability assay can be used as a commercial test with a lyophilized inoculum in order to monitor the ready biodegradability of an organic pollutant or a WWTP influent. Moreover, a combination of the BOD₅/COD ratio and the P. putida biodegradability test is an attractive alternative in order to evaluate the biodegradability enhancement in water pre-treated with advanced oxidation processes (AOPs).     

Probability analyses of combining background concentrations with model-predicted concentrations

In order to calculate total concentrations for comparison to ambient air quality standards, monitored background concentrations are often combined with model predicted concentrations. Models have low skill in predicting the locations or time series of observed concentrations. Further, adding fixed points on the probability distributions of monitored and predicted concentrations is very conservative and not mathematically correct. Simply adding the 99th percentile predicted to the 99th percentile background will not yield the 99th percentile of the combined distributions. Instead, an appropriate distribution can be created by calculating all possible pairwise combinations of the 1-hr daily maximum observed background and daily maximum predicted concentration, from which a 99th percentile total value can be obtained. This paper reviews some techniques commonly used for determining background concentrations and combining modeled and background concentrations. The paper proposes an approach to determine the joint probabilities of occurrence of modeled and background concentrations. The pairwise combinations approach yields a more realistic prediction of total concentrations than the U.S. Environmental Protection Agency's (EPA) guidance approach and agrees with the probabilistic form of the National Ambient Air Quality Standards.

Implications: EPA's current approaches to determining background concentrations for compliance modeling purposes often lead to “double counting” of background concentrations and actual plume impacts and thus lead to overpredictions of total impacts. Further, the current Tier 1 approach of simply adding the top ends of the background and model predicted concentrations (e.g., adding the 99th percentiles of these distributions together) results in design value concentrations at probabilities in excess of the form of the National Ambient Air Quality Standards.     

Particulate matter speciation profiles for light-duty gasoline vehicles in the United States

Representative profiles for particulate matter particles less than or equal to 2.5 µm (PM_2.5) are developed from the Kansas City Light-Duty Vehicle Emissions Study for use in the U.S. Environmental Protection Agency (EPA) vehicle emission model, the Motor Vehicle Emission Simulator (MOVES), and for inclusion in the EPA SPECIATE database for speciation profiles. The profiles are compatible with the inputs of current photochemical air quality models, including the Community Multiscale Air Quality Aerosol Module Version 6 (AE6). The composition of light-duty gasoline PM_2.5 emissions differs significantly between cold start and hot stabilized running emissions, and between older and newer vehicles, reflecting both impacts of aging/deterioration and changes in vehicle technology. Fleet-average PM_2.5 profiles are estimated for cold start and hot stabilized running emission processes. Fleet-average profiles are calculated to include emissions from deteriorated high-emitting vehicles that are expected to continue to contribute disproportionately to the fleet-wide PM_2.5 emissions into the future. The profiles are calculated using a weighted average of the PM_2.5 composition according to the contribution of PM_2.5 emissions from each class of vehicles in the on-road gasoline fleet in the Kansas City Metropolitan Statistical Area. The paper introduces methods to exclude insignificant measurements, correct for organic carbon positive artifact, and control for contamination from the testing infrastructure in developing speciation profiles. The uncertainty of the PM_2.5 species fraction in each profile is quantified using sampling survey analysis methods. The primary use of the profiles is to develop PM_2.5 emissions inventories for the United States, but the profiles may also be used in source apportionment, atmospheric modeling, and exposure assessment, and as a basis for light-duty gasoline emission profiles for countries with limited data.

Implications: PM_2.5 speciation profiles were developed from a large sample of light-duty gasoline vehicles tested in the Kansas City area. Separate PM_2.5 profiles represent cold start and hot stabilized running emission processes to distinguish important differences in chemical composition. Statistical analysis was used to construct profiles that represent PM_2.5 emissions from the U.S. vehicle fleet based on vehicles tested from the 2005 calendar year Kansas City metropolitan area. The profiles have been incorporated into the EPA MOVES emissions model, as well as the EPA SPECIATE database, to improve emission inventories and provide the PM_2.5 chemical characterization needed by CMAQv5.0 for atmospheric chemistry modeling.     

Utilization of Cellulosic Wastes in Textile and Garment Industries: 2. Synthesis and Characterization of Cellulose Acetate from Knitted Rag

Cellulose acetate (CA) was synthesized from knitted rag, a cellulosic waste of Textile and Garment industries, in the glacial acetic acid, and subsequently acetic anhydride (Ac₂O) in presence of concentrated H₂SO₄ reaction medium. A low to high substitution products were obtained from single step up to seven steps acetylation of cellulose. In this way, it was possible to produce low cost and different grades or substituted acetylation derivatives of cellulose. The synthesized CA was characterized and investigation of its physical characteristics was done. Solubility, acetyl content, acetic acid content, degree of substitution, and molecular weight of CA increased gradually with the increase of the number of reaction steps attaining optimum value at the fourth step. The acetyl and acetic acid content of CA were increased from 39.95 % to 44.25 %, and from 55.73 % to 61.73 % respectively. Similarly, degree of substitution and molecular weight of CA were increased from 2.47 to 2.94, and from 74,249 to 121,437 respectively.     

Oxidative stress and biochemical perturbations induced by insecticides mixture in rat testes

The joint action of pyrethroids, lambda-cyhalothrin (LC) in combination with organophosphates, fenitrothione (FNT) on antioxidant defense system and lipid peroxidation biomarkers in rat testes was studied. The results suggest that incubation of testes homogenate with different concentrations of insecticide mixture for different time intervals significantly decreased the activity of antioxidant enzymes, like glutathione S-transferase (GST), superoxide dismutase (SOD) and catalase (CAT), and the level of reduced glutathione (GSH). In addition, a significant inhibition in transaminases (AST, ALT), phosphatases (AcP, AlP) activity and protein content were observed. On the other hand, FNT plus LC increased the cellular lipid peroxidation (LPO) level and the activity of lactate dehydrogenase (LDH). In conclusion, the use of insecticides mixture might cause marked oxidative damage in a concentration and time-dependent manner.     

Effects of combinations of malathion and cypermethrin on survivability and time of metamorphosis of tadpoles of Indian cricket frog (Fejervarya limnocharis)

This study was undertaken to determine the effect of environmentally realistic concentrations of two commonly used pesticides viz., malathion and cypermethrin, using a fully 3 × 3 factorial experiments on the survivability and time of metamorphosis in a common rice paddy field frog (cricket frog) Fejervarya limnocharis under laboratory conditions. The results suggest that cypermethrin is more toxic than malathion and combinations of higher concentrations of cypermethrin (50 μg/L) with malathion (250 and 500 μg/L) are more deleterious to the survivability of tadpoles. With increasing cypermethrin concentration, the survivability of tadpole decreased (r = ?0.986, P = 0.108). But cypermethrin alone induced early metamorphosis among the surviving tadpoles. However, there was a delay in the time required for metamorphosis induced by malathion and its combination with cypermethrin. The delay in metamorphosis may indicate the altered physiological fitness of the individual. The emergent froglets will be subjected to environmental stressors like high temperature and less humidity of post-monsoon tropical climate that could enhance negative influence triggered by pesticides.