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Evaluation of natural and enhanced PCP biodegradation at a former pesticide manufacturing plant.

Pentachlorophenol (PCP) has been used in the past as a pesticide, herbicide, antifungal agent, bactericide, and wood preservative. Thus, PCP is among the most ubiquitous chlorinated compounds found in groundwater contamination. A former pesticide manufacturing plant located in southern Taiwan has been identified as a PCP spill site. In this study, groundwater samples collected from the PCP site were analyzed to assess the occurrence of natural PCP biodegradation. Microcosm experiments were conducted to (1) evaluate the feasibility of biodegrading PCP by indigenous microbial consortia under aerobic and cometabolic conditions, and (2) determine the potential of enhancing PCP biodegradation using cane molasses and biological sludge cake as the substitute primary substrates under cometabolic conditions. The inocula used in this microcosm study were aquifer sediments collected from the PCP site and activated sludges collected from the municipal and industrial wastewater treatment plants. Results from this field investigation indicate that the natural biodegradation of PCP is occurring and causing the decrease in PCP concentration. Microcosm results show that the indigenous microorganisms can biodegrade PCP under both aerobic and aerobic cometabolism conditions. A PCP-degrading bacterium was isolated from the collected aquifer sediments and identified as Pseudomonas mendocina NSYSU via some biochemical tests and further conformation of DNA sequencing. In batch cultures, P. mendocina NSYSU used PCP as its sole source of carbon and energy. The isolated bacterium, P. mendocina NSYSU, was capable of completely degrading PCP as indicated by the increase in biomass formation with the decrease in PCP concentrations occurred in the carbon-free medium simultaneously. Results indicate that the in situ or on-site aerobic bioremediation using indigenous microorganisms or inoculated bacteria would be a feasible technology to clean up the studied PCP-contaminated site. Results from this study will be useful in designing a scale-up in situ or on-site PCP bioremediation system (e.g., on-site bioreactor) for field application.

Accidents↗

Inactivation of enteric microorganisms with chemical disinfectants, UV irradiation and combined chemical/UV treatments.

The relative disinfection efficiencies of peracetic acid (PAA), hydrogen peroxide (H2O2) and sodium hypochlorite (NaOCl) against Escherichia coli, Enterococcus faecalis, Salmonella enteritidis and coliphage MS2 virus were studied in laboratory-scale experiments. This study also evaluated the efficiency of combined PAA/ultraviolet irradiation (UV) and H2O2/UV treatments to determine if the microbial inactivation was synergistic. Microbial cultures were added into a synthetic wastewater-like test medium and treated by chemical disinfectants with a 10 min contact time, UV irradiation or the combination of chemical and UV treatments. A peracetic acid dose of 3 mg/l resulted in approximately 2-3 log enteric bacterial reductions, whereas 7-15 mg/l PAA was needed to achieve 1-1.5 log coliphage MS2 reductions. Doses of 3-150 mg/l hydrogen peroxide achieved below 0.2 log microbial reductions. Sodium hypochlorite treatments caused 0.3-1 log microbial reductions at an 18 mg/l chlorine dose, while 2.6 log reductions of E. faecalis were achieved at a 12 mg/l chlorine dose. The results indicate that PAA could represent a good alternative to chlorine compounds in disinfection procedures, especially in wastewaters containing easily oxidizable organic matter. Hydrogen peroxide is not an efficient disinfectant against enteric microorganisms in wastewaters. The combined PAA/UV disinfection showed increased disinfection efficiency and synergistic benefits with all the enteric bacteria tested but lower synergies for the coliphage MS2. This suggests that this method could improve the efficiency and reliability of disinfection in wastewater treatment plants. The combined H2O2/UV disinfection only slightly influenced the microbial reductions compared to UV treatments and showed some antagonism and no synergies.

Disinfectants↗

Chemometrics in monitoring spatial and temporal variations in drinking water quality.

This case study reports multivariate techniques applied for the evaluation of temporal/spatial variations and interpretation of monitoring data obtained by the determination of chloro/bromo disinfection by-products in drinking water at 12 locations in the Gdańsk area (Poland), over the period 1993-2000. The complex data matrix (1756 observations) was treated with various multivariate techniques. Cluster analysis (CA) was successful, yielding two different groups of similarity reflecting different types of drinking water supplied (surface and groundwater). The locations supplied in general with groundwater could be further classified into two subgroups, depending on whether the groundwater was mixed with surface water or not. Analysis of variance (ANOVA) was used to classify and thus confirm the groups found by means of cluster analysis and proved the existence of statistically significant differences between the concentration levels of CHCl3, CHBrCl2+C2HCl3, CHBr2Cl, and CH2Cl2 in the samples collected. Of all the variables evaluated, only three were characterized by statistically significant correlations (CHCl3, CHBrCl2+C2HCl3, CHBr2Cl). The analysis of correlation coefficients revealed that chloroform formed as the main chlorinated disinfection by-product and, furthermore, the natural presence of bromide in water (both ground and surface) results in the formation of brominated disinfection by-products (DBPs). Temporal variations of volatile organic chlorinated compounds (VOCls) were also evaluated by multidimensional ANOVA. Observation of temporal changes in the concentration of VOCls at the location supplied with both surface and groundwater reveals a steady improvement in drinking water quality. In general, the study shows the importance of drinking water monitoring in connection with simple but powerful statistical tools to better understand spatial and temporal variations in water quality.

Cluster Analysis↗

Systematic review of microorganism disinfection performance by chemical and ultraviolet light water treatment methods.

Safe drinking water is critical for public health, yet microbial contamination remains a significant global challenge. We conducted a systematic review to update World Health Organization guidance on water disinfection technologies by synthesizing peer-reviewed literature from 1997 to 2021 on the performance of free chlorine, chlorine dioxide, ozone, and ultraviolet (UV) light against bacteria, viruses, and protozoa. Following PRISMA guidelines, we analyzed log10 reduction values (LRVs) and contact times (Ct) or fluence (for UV) from laboratory and field studies. We included studies from multiple databases and expert-recommended studies. Results show mean Cts for 2 LRV of non-opportunistic bacteria as 6.0 (free chlorine), 0.4 (chlorine dioxide), and 1.2 (ozone) mg/L*min, and a mean UV fluence of 8.2 mJ/cm² (all bacteria). Viruses required lower Cts, except for UV-resistant adenoviruses, while protozoa required higher Cts or fluences. Opportunistic bacteria required significantly higher Cts than non-opportunistic bacteria for free chlorine and chlorine dioxide. Temperature and pH effects were inconsistent, highlighting data variability and gaps in field studies. These findings support global guidance on water treatment and may be used alongside other context-specific data to understand the roles these technologies play in reducing waterborne exposures. We recommend standardized reporting from performance studies to enable straightforward synthesis of evidence.

Disinfection↗

Membrane phosphorylation protects the cardiac sarcoplasmic reticulum Ca(2+)-ATPase against chlorinated oxidants in vitro.

OBJECTIVE: The calcium (Ca) pump of cardiac sarcoplasmic reticulum (SR) membranes is vulnerable to oxidation and hence likely to be damaged by chlorinated compounds, specifically hypochlorite (NaOCl) and monochloramine (NH2Cl), the most potent oxidants produced upon neutrophil activation. This could occur during prolonged ischemia or myocardial infarction when tissue levels of catecholamines are high. Phospholamban (PLN), the phosphorylatable regulator of the Ca pump, plays a central role in the effects of beta-adrenergic agonists on the heart. The purpose of this study was to investigate a possible role of PLN in determining the pump's sensitivity to NaOCl and NH2Cl. METHODS: Ca-uptake and Ca(2+)-ATPase activities in purified phosphorylated and control canine cardiac microsomes, incubated at increasing concentrations of NaOCl or NH2Cl, were related to the extent of PLN phosphorylation by protein kinase A, which was quantitated by PhosphorImager analysis. RESULTS AND CONCLUSIONS: Our data indicate that microsomal phosphorylation protects the Ca pump fully against 10 microM NaOCl or NH2Cl, which inhibit Ca-uptake by 21-41% when assayed at 25 or 37 degrees C and saturating Ca2+ in unphosphorylated microsomes, and protects partially at higher oxidant concentrations. The protective effect of protein kinase A on Ca-uptake is proportional to the amount of phosphorylated PLN. No comparable protection against similar oxidative damage of the Ca pump is observed when light fast skeletal muscle microsomes, which lack PLN, are incubated under conditions favorable for phosphorylation nor when PLN's inhibition of the cardiac Ca pump is relieved by proteolytic cleavage of its cytoplasmic domain. Our findings contribute toward an understanding of possible endogenous protective mechanisms that may promote calcium homeostasis in myocardial cells in inflammatory states associated with neutrophil activation and may suggest an approach toward development of protective strategies against oxidative damage in the heart.

Ammonium Chloride↗

Determination of aromatic amines in water samples by capillary electrophoresis with electrochemical and fluorescence detection.

Two capillary electrophoresis methods have been compared for the determination of aniline derivatives in environmental water samples. With the first method the anilines were separated as cations by free zone electrophoresis at low pH, and detected by amperometry. For this, the separation capillary was connected through a palladium field decoupler to an electrochemical detection cell which had been modified to match the volume scale of the separation. Most anilines tested, except chlorinated compounds, could be detected with full sensitivity at a detection potential of +0.7 V. Detection limits with this detection scheme were on a low microg/l level. The alternative method involved the derivatization of the anilines with fluorescamine, the separation of the derivatives formed by micellar electrokinetic chromatography, and fluorescence detection. For detection a lamp-based, fibre optics instrument was used. Detection limits with fluorimetry were comparable with those obtained with amperometric detection (in the order of 1 microg/l). Still, this method was preferred since it gave a higher separation efficiency and shorter analysis times (approximately 4 min). The most important argument, however, was its higher reliability and ease-of-handling. Preliminary experiments with water samples collected in areas where pollution with anilines may be expected showed that the method is highly specific, with few interferences showing up in the electropherograms.

Amines↗

High-performance liquid chromatographic method for isolating organic contaminants from tissue and sediment extracts.

Interest in the assessment of the anthropogenic contamination of the marine environment has accelerated in recent years. Existing methods to analyze environmental samples (e.g., sediments or tissues) for trace amounts of organic contaminants such as aromatic hydrocarbons and chlorinated compounds are tedious and costly. We report a rapid, efficient high-performance liquid chromatography (HPLC) procedure which uses a size-exclusion column to separate the analytes of interest from interfering compounds in the sample matrix. Analytical results from the HPLC method were, in general, comparable to a gravity-column method which had been used for several years. The HPLC method had several other advantages: improved precision; the ability to monitor chromatographic conditions; the potential for automating analyses; and reduced consumption of solvents and other materials.

Animals↗

A chlorinated amide and piperidine alkaloids from Aloe sabaea.

Phytochemical investigations of Aloe sabaea afforded a new chlorinated amide, N-4'-chlorobutylbutyramide, and the toxic piperidine alkaloids coniine, gamma-coniceine and the quarternary N,N-dimethylconiine. This is the first report of the occurrence of a chlorinated compound in the Aloeaceae family.

Alkaloids↗

Sesquiterpene lactones of Centaurea scoparia.

From the ethanolic extract of the aerial parts of Centaurea scoparia four new sesquiterpene lactones, belonging to the guaiane class, were isolated and identified, together with a known germacranolide. The structures were elucidated by spectroscopic methods including one- and two-dimensional NMR studies. The relative configuration was deduced from the 2D NOESY spectra. CD spectroscopy of the chlorinated compounds was used for determination of their absolute configuration.

Journal Article↗

Remediation of PCE-contaminated aquifer by an in situ two-layer biobarrier: laboratory batch and column studies.

The industrial solvent tetrachloroethylene (PCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop an in situ two-layer biobarrier system consisting of an organic-releasing material layer followed by an oxygen-releasing material layer. The organic-releasing material, which contained sludge cakes from a domestic wastewater treatment plant, is able to release biodegradable organics continuously. The oxygen-releasing material, which contained calcium peroxide, is able to release oxygen continuously upon contact with water. The first organic-releasing material layer was to supply organics (primary substrates) to reductively dechlorinate PCE in situ. The second oxygen-releasing material layer was to release oxygen to aerobic biodegrade or cometabolize PCE degradation byproducts from the first anaerobic layer. Batch experiments were conducted to design and identify the components of the organic and oxygen-releasing materials, and evaluate the organic substrate (presented as chemical oxygen demand (COD) equivalent) and oxygen release rates from the organic-releasing material and oxygen-releasing materials, respectively. The observed oxygen and COD release rates were approximately 0.0368 and 0.0416 mg/d/g of material, respectively. A laboratory-scale column experiment was then conducted to evaluate the feasibility of this proposed system for the bioremediation of PCE-contaminated groundwater. This system was performed using a series of continuous-flow glass columns including a soil column, an organic-releasing material column, two consecutive soil columns, and an oxygen-releasing material column, followed by two other consecutive soil columns. Anaerobic acclimated sludges were inoculated in the first four columns, and aerobic acclimated sludges were inoculated in the last three columns to provide microbial consortia for contaminant biodegradation. Simulated PCE-contaminated groundwater with a flow rate of 0.25 L/d was pumped into this system. Effluent samples from each column were analyzed for PCE and its degradation byproducts. Results show that up to 99% of PCE removal efficiency was obtained in this passive system. Thus, the biobarrier treatment scheme has the potential to be developed into an environmentally and economically acceptable remediation technology for the in situ treatment of PCE-contaminated aquifer.

Bacteria, Aerobic↗

Development of a biobarrier for the remediation of PCE-contaminated aquifer.

The industrial solvent tetrachloroethylene (PCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop a biobarrier system, which includes a peat layer to enhance the anaerobic reductive dechlorination of PCE in situ. Peat was used to supply primary substrate (electron donor) continuously. A laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system or PCE removal. This experiment was performed using a series of continuous-flow glass columns including a soil column, a peat column, followed by two consecutive soil columns. Anaerobic acclimated sludges were inoculated in all three soil columns to provide microbial consortia for PCE biodegradation. Simulated PCE-contaminated groundwater with a flow rate of 0.25 l/day was pumped into this system. Effluent samples from each column were analyzed for PCE and its degradation byproducts (trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), vinyl chloride (VC), ethylene (ETH), and ethane). Results show that the decrease in PCE concentrations and production of PCE byproducts were observed over a 65-day operating period. Up to 98%, of PCE removal efficiency was obtained in this passive system. Results indicate that the continuously released organics from peat column enhanced PCE biotransformation. Thus, the developed biobarrier treatment scheme has the potential to be developed into a cost-effective in situ PCE-remediation technology, and can be utilized as an interim step to aid in system scale-up.

Biotransformation↗

Laboratory column studies for evaluating a barrier system for providing oxygen and substrate for TCE biodegradation.

The industrial solvent trichloroethylene (TCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop a biobarrier system containing oxygen-organic releasing material to enhance the aerobic cometabolism of TCE in situ. The oxygen-organic material, which contains calcium peroxide and peat, is able to release oxygen and primary substrates continuously upon contact with water. Batch experiments were conducted to design and identify the components of the oxygen-organic releasing material, and evaluate the oxygen and organic substrate (presented as COD equivalent) release from the designed oxygen-organic material. The observed oxygen and chemical oxygen demand (COD) release rates were approximately 0.0246 and 0.052 mg/d/g of material, respectively. A laboratory-scale column experiment was then conducted to evaluate the feasibility of this proposed system for the bioremediation of TCE-contaminated groundwater. This system was performed using a series of continuous-flow glass columns including a soil column, an oxygen-organic material column, followed by two consecutive soil columns. Aerobic acclimated sludges were inoculated in all three soil columns to provide microbial consortia for TCE biodegradation. Simulated TCE-contaminated groundwater with a flow rate of 0.25 l/day was pumped into this system. Effluent samples from each column were analyzed for TCE and other indicating parameters (e.g., pH, dissolved oxygen). Results show that the decreases in TCE concentrations were observed over a 4-month operating period. Up to 99% of TCE removal efficiency was obtained in this passive system. Results indicate that the continuously released oxygen and organic substrates from the oxygen-organic materials enhanced TCE biotransformation. Thus, the biobarrier treatment scheme has the potential to be developed into an environmentally and economically acceptable remediation technology.

Biodegradation, Environmental↗

Effects of copper chloride on formation of polychlorinated dibenzofurans in model waste incineration in a laboratory-scale fluidized-bed reactor.

Combustion experiments in a laboratory-scale fluidized-bed reactor have been performed to clarify the effects of copper chloride as a catalyst on polychlorinated dibenzofurans (PCDFs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl2 x 2H2O) as a catalyst, both of which contained polyvinyl chloride (PVC) as a chlorine source. Combustion temperature was set to 900 degrees C, and the amount of air supplied was twice as much as the theoretical amount. The experimental setup had been carefully planned to ensure avoidance of the influences of previous experiments. Results of these present experiments revealed that copper chloride in the waste increased the amount of PCDFs formed and made the homologue profile shifted towards the highly chlorinated species. Copper chloride contributes to PCDFs formation by promoting chlorination via catalytic reactions, whereby the reaction could be important in that organic matters are chlorinated directly by chlorinated compounds related to Deacon reaction such as copper chloride. It was elucidated that characteristic isomer distribution patterns appeared in case the waste contained copper chloride. It is probable in our experiment with copper chloride that PCDFs are mainly formed via catalytic reactions of copper compounds and carbon.

Benzofurans↗

Polychlorinated diphenyl ethers, dibenzo-p-dioxins, dibenzofurans and biphenyls in seals and sediment from the Gulf of Finland.

Polychlorinated diphenyl ethers (PCDEs), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) were analyzed in seals from the Gulf of Finland and in sediments from the Gulf of Finland and near Gotland. The sediments included one surface core from both sampling sites. The seal material consisted of 14 ringed seals and 6 grey seals that all were found dead and examined for pathology. The main aims were to scrutinize levels and patterns of PCDEs for the first time in seals from the Baltic Sea and to estimate whether chlorinated compounds mentioned have an influence on an exceptional high mortality that occurred among ringed seals in the Gulf of Finland in late 1991. The concentrations of 50 congeners of tetra- through deca-CDEs analyzed ranged from < 0.3 to 62 ng/g lipid weight (lw) in seal blubber, but in the sediments PCDEs were non-detectable (tetra- through hepta-CDEs < 0.1 ng/g dry weight (dw)). In ringed seals with good nutritional status, the concentrations of almost all PCDE congeners were greater in two adult females than in specimens of younger age groups. The concentrations of PCDDs and PCDFs as TCDD-equivalents exceeded those of the coplanar (non-ortho) PCBs in sediments, whereas non- and monoortho PCBs constituted greater toxic loads as those calculated for PCDDs and PCDFs in seals. However, the levels revealed do not explain the high mortality of ringed seals.

Adipose Tissue↗

Treatment of PCB-contaminated soil in a pilot-scale continuous decomposition system.

The BCDP (Base Catalyzed Decomposition Process) is a process by which difficult-to-decompose organic chlorine compounds, such as PCBs, are chemically decomposed and dechlorinated. Pilot-plant tests for PCB contaminated soil were carried out. PCB contaminated soil (32 mg/kg-530 mg/kg) was decontaminated to a level (0.038 mg/kg-4.8 mg/kg) which satisfied the corresponding Japanese environmental standard which stipulates, "there must be no discharge of PCB containing leachate".

Environmental Pollution↗

On the degradability of tetrachloroethene in biologically treated wastes.

Investigation on the degradability of tetrachloroethene was performed using fresh and mechanically-biologically pretreated household waste. The corresponding metabolites were determined and the experimental conditions were characterized by the concentrations of methane, organic acids, sulfate and nitrate as well as by pH and redox potential. Furthermore, sorption studies on the substances in different wastes were carried out. With pretreated waste the degradation efficiency was much higher than with fresh waste. On the other hand, the fresh waste showed higher sorption capacity for the chlorinated compounds.

Biodegradation, Environmental↗

Application of a purge and trap TDS-GC/MS procedure for the determination of emissions from flame retarded polymers.

Emissions of volatile organic compounds (VOCs) from different thermoplastic polymers used in electrotechnical applications were investigated using a purge and trap procedure that involved adsorption on Tenax GR. Results were compared to those for an operating TV set monitored in a test chamber. The analyses were in both cases carried out using thermodesorption gas chromatography with mass spectrometric detection (TDS-GC/MS). Substances identified were monomers, volatile additives, or related compounds. Special attention was given to the detection of halogenated compounds. Their origin was studied using reference samples and synthetic standards.

Air Pollutants↗

Chlorinated pesticides and polychlorinated biphenyls in marine tucuxi dolphins (Sotalia fluviatilis) from the Cananéia estuary, southeastern Brazil.

The Cananéia estuary is an important biological area on the southeast coast of Brazil. In the past, it was impacted by both chlorinated pesticides and polychlorinated biphenyls (PCBs) due to its natural location. The marine tucuxi dolphin (Sotalia fluviatilis) is a top predator in this ecosystem and can be found year round in Cananéia estuarine waters that represent an important nursing area for the species. This work investigated chlorinated compounds in the blubber of nine individuals from the Cananéia estuary. Residue levels of DDTs (0.541-125 microg g(-1) lipid wt.) were the highest, followed by PCBs (0.2-9.22 microg g(-1) lipid wt.), mirex (0.014-0.312 microg g(-1) lipid wt.), chlordanes (0.001-0.047 microg g(-1) lipid wt.), HCHs (<0.003-0.044 microg g(-1) lipid wt.), and HCB (n.d.-0.024 microg g(-1) lipid wt.). The mean p,p'-DDE/Sigma DDT ratio was approximately 0.8 and is indicative of the former DDT application in the study area. PCB contamination is suggested to be associated with atmospheric transport and relative proximity to the Cubatão industrial complex-the most important along the Brazilian coast. Low levels of HCHs and HCB can be attributed to their high volatility in tropical environments. Concentrations of organochlorines in the blubber of marine tucuxis from the Cananéia estuary were lower than levels found in small cetacean species from developed countries, where the input of these compounds was considerably greater than in Brazil. At extremes, male dolphins can present DDT burden several orders of magnitude higher than females. Despite the high levels of total DDT found in males, the major detected compound was p,p'-DDE which is considered to be of low toxicity.

Adipose Tissue↗