Photodegradation of pentachlorophenol by sunlight in aquatic surface microlayers

Photodegradation of pentachlorophenol (PCP) in aquatic surface microlayer (SM) was examined under natural sunlight. SM samples were collected using a glass plate, along with corresponding subsurface waters. PCP was added to samples of the SM and subsurface water. When all samples were exposed to the same natural sunlight conditions, the first order photodegradation rates of PCP in the SM water samples were different from those of PCP in corresponding subsurface water samples. The difference was correlated with the enrichment of dissolved organic carbon (DOC) in SM compared to the corresponding subsurface waters. Enhanced photodegradation in SM may be due to increased abundance of photoreactants related to the UV-absorbing properties of dissolved organic materials in the SM as the result of photo-induced reactions. Effects of environmental factors, pH and salinity, on photodegradation process of PCP in SM were also evaluated.     

A kinetic study on oxidation of pentachlorophenol by ozone

The kinetics of pentachlorophenol (PCP) ozonation in terms of the gaseous O3 and dissolved PCP concentrations has been investigated. When the O3 concentration in the gas phase was in the range of 10 to 40 g O3/m3, the O3 dissolved for a short time period was proportional to the gaseous O3 concentration. In this range, the ozonation reaction was first order for each reactant and the overall reaction was second order. At 25 degrees C, in an aqueous solution, the reaction rate constant was estimated to be 10.048 L/mol.sec. The reaction rate was much greater than the mass-transfer rate, indicating that the reaction of O3 and PCP was an interface reaction on the surface of gaseous O3 bubbles. The final product of the PCP ozonation was oxalic acid, with the carbon yield of the reaction being 59.4%. The ozonation of PCP in the aqueous solution was not a radical reaction but a direct reaction between O3 and PCP molecules under the conditions investigated in this study, since O3 has a high selectivity toward PCP. The reaction rate increased with the reaction temperature up to 35 degrees C but decreased at temperatures greater than 35 degrees C due to the decreased solubility of O3. The addition of H2O2 did not increase the reaction rate significantly.     

Environmental fate of rice paddy pesticides in a model ecosystem.

The distribution and metabolic fate of several rice paddy pesticides were evaluated in a modified model ecosystem. Among the three BHC isomers, beta-isomer was the most stable and bioconcentrated in all of the organisms. Alpha- and gamma-isomers were moderately persistent and degraded to some extent during the 33 day period. Disulfoton was relatively persistent due to the transformation to its oxidation products. Pyridaphenthion was fairly biodegradable. N-Phenyl maleic hydrazide derived from the hydrolysis of pyridaphenthion was not detected in the organisms though it was found in the aquarium water after 33 days. Cartap and edifenphos were considerably biodegradable, and the ratio of the conversion to water soluble metabolites was very high. There was a distinct difference in the persistence of Kitazin P and edifenphos in the aquarium water. It appeared that the hydrolysis rate of the pesticides affected their fate in the organisms. PCP appeared to be moderately biodegradable. CNP was considerably stable and stored in the organisms though the concentration in the aquarium water was relatively low. The persistence and distribution of the pesticides in the model ecosystem were dependent on their chemical structures. In spite of the limitation derived from short experimental period, the model ecosystem may be applicable for predicting the environmental fate of pesticides.     

Isolation and physiological characterization of the pentachlorophenol degrading bacterium Sphingomonas chlorophenolica

Many chlorophenols tend to persist in the environment, and they may become public health hazards. Among chlorophenols, pentachlorophenol (PCP) is a priority pollutant that has been used widely as a general biocide in commercial wood treatment. Owing to the rapid industrial growth, serious soil and water pollutions by chlorophenols has been reported in Taiwan. In this study, 10 indigenous PCP-degrading bacterial strains were isolated from a PCP-degrading mixed culture, and the potential of both the pure and mixed cultures for PCP degradation compared. Moreover, the physiological characteristics and optimum growth conditions of the PCP-degrading bacteria were investigated. One of the isolated bacterial strains with good potential for PCP degradation was characterized and identified as Sphingomonas chlorophenolica by 16S rDNA gene analysis. The result of the optimum growth temperatures revealed that this organism was a mesophile. The optimum pH for PCP removal by S. chlorophenolica was between 6.9 and 7.6. Increase in concentration of PCP has a negative effect on the biodegradation potential of S. chlorophenolica and PCP concentration above 600 mg l(-1) was inhibitory to its growth. The results of this study indicate that this S. chlorophenolica strain has a better potential for PCP degradation compared to the enriched mixed culture. The physiological characterization of the isolates also indicates the possible application of this strain for bioremediation of sites contaminated with PCP.     

Distribution and bioaccumulation of selenium in aquatic microcosms

Closed-system microcosms were used to study factors affecting the fate of selenium (Se) in aquatic systems. Distribution and bioaccumulation of Se varied among sediment types and Se species. A mixture of dissolved (75)Se species (selenate, selenite and selenomethionine) was sorbed more rapidly to fine-textured, highly organic pond sediments than to sandy riverine sediments. Sulfate did not affect the distribution and bioaccumulation of (75)Se over the range 80-180 mg SO(4) liter(-1). When each Se species was labeled separately, selenomethionine was lost from the water column more rapidly than selenate or selenite. Selenium lost from the water column accumulated primarily in sediments, but volatilization was also an important pathway for loss of Se added as selenomethionine. Loss rates of dissolved Se residues were more rapid than rates reported from mesocosm and field studies, suggesting that sediment: water interactions are more important in microcosms than in larger test systems. Daphnids accumulated highest concentrations of Se, followed by periphyton and macrophytes. Selenium added as selenomethionine was bioaccumulated preferentially compared to that added as selenite or selenate. Organoselenium compounds such as selenomethione may thus contribute disproportionately to Se bioaccumulation and toxicity in aquatic organisms.     

消毒剂和溶解氧对管网铁释放影响的中试研究

针对南水北调中线水源地丹江口水库水调入受水区城市后,可能引起管网铁腐蚀产物释放的问题,从北方某受水区城市的实际管网中挖取了原通地下水的3个地点的铸铁管道,在丹江口搭建了中试模拟系统,开展水源切换以及消毒剂和溶解氧对管网铁释放影响的中试研究。结果表明,实验管道管垢较薄且稳定性较差,在水源切换初期有"黄水"现象发生;增加进水硫酸根浓度,管网系统出水总铁浓度和浊度均有所增加;在0.3~3.6 mg/L的范围内改变进水自由氯浓度对实验系统铁释放的影响没有明显的规律;但进水氯胺浓度从1.3 mg/L增加到2.0 mg/L时,YS系统的铁释放有所升高;进水溶解氧浓度从8 mg/L增加到15 mg/L时,实验系统的铁释放都有明显的降低,但再增加到20 mg/L时,铁释放反而有所升高。     

Simulation of long-term environmental dynamics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans using the dynamic multimedia environmental fate model and its implication to the time trend analysis of dioxins

Long term environmental fate of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were studied using the fugacity-based dynamic multimedia environmental fate model. New formulation about soil wind erosion into air was included into the model. Effect of process assumption, sensitivity analysis for parameters, and tentative validation against the measured sediment core analysis was performed. Mass fluxes between compartments were estimated by the dynamic modeling. From the model estimates, major mass fluxes coming from emission source were shown to go to the soil and water through wet/dry deposition, then go to degradation mainly in the soil and sediment. Major mass fluxes of TCDD and OCDD come from the impurities in CNP (Chlornitrofen) and PCP (Pentachlorophenol) directly into the soil. Consideration about multimedia environmental dynamics using the modeled mass fluxes was shown in the discussion.     

Analysis of marine sediment, water and biota for selected organic pollutants

The concentrations of various organic pollutants (benzo(a)pyrene (BaP), hexachlorobenzene (HCB) and pentachlorophenol (PCP)) were determined in samples of water, sediment and biota (flounder, killifish, shrimp, crabs and squid) from San Luis Pass, Texas. Sediment was also analyzed for polychlorinated biphenyls (PCBs), phthalic acid esters (PAEs) and various pesticides. Only PCP was detectable in water. In sediment, the relative concentrations were PAEs > BaP > (PCBs HCB) > PCP. In biota, BaP was not detectable in any animal; HCB was highest in crabs and PCP was highest in all others (flounder, killifish, shrimp and squid). The relative concentrations of HCB and PCP were different in the different organisms. The differences between the relative concentrations in the biota and in sediment are discussed. The results of this study are compared to values measured at other sites. This study is part of a larger effort to identify and quantitate pollutants in various Texas estuaries and to serve as a basis for monitoring marine pollution.     

Can adsorption isotherms predict sediment bioavailability?

The adsorption and desorption of 2,4-dichlorophenol (DCP) and pentachlorophenol (PCP) were studied for a range of synthetic particles, a dimethylditallowammonium exchanged clay and a natural sediment. The synthetic particles were Dowex 1X8400, Toyopearl Phenyl 650M and Toyopearl SP 650M. The bioaccumulation of the DCP and PCP from these particles was then studied using the oligochaete, Lumbriculus variegatus. There is a correlation between contaminant-particle interactions, as determined from adsorption and desorption isotherms, and bioaccumulation. Bioaccumulation by L. variegatus was found to be highest from the systems where differences in the classification of adsorption and desorption isotherms were observed.     

1990 Government Agencies Directory

ABSTRACT

The kinetics of pentachlorophenol (PCP) ozonation in terms of the gaseous O₃ and dissolved PCP concentrations has been investigated. When the O₃ concentration in the gas phase was in the range of 10 to 40 g O₃/m³, the O₃ dissolved for a short time period was proportional to the gaseous O₃ concentration. In this range, the ozonation reaction was first order for each reactant and the overall reaction was second order. At 25 °C, in an aqueous solution, the reaction rate constant was estimated to be 10.048 L/mol-sec. The reaction rate was much greater than the mass-transfer rate, indicating that the reaction of O₃ and PCP was an interface reaction on the surface of gaseous O₃ bubbles. The final product of the PCP ozonation was oxalic acid, with the carbon yield of the reaction being 59.4%. The ozonation of PCP in the aqueous solution was not a radical reaction but a direct reaction between O₃ and PCP molecules under the conditions investigated in this study, since O₃ has a high selectivity toward PCP. The reaction rate increased with the reaction temperature up to 35 °C but decreased at temperatures greater than 35 °C due to the decreased solubility of O₃. The addition of H₂O₂ did not increase the reaction rate significantly.     

Mercury concentration in black flies Simulium spp. (Diptera, Simuliidae) from soft-water streams in Ontario, Canada

Total Hg in Simulium spp. (Diptera, Simuliidae) was measured in 17 soft-water streams in the District of Muskoka and Haliburton County (Ontario, Canada) during 2003 and 2004. Black flies contained 0.07-0.64 microg/g total Hg (dry weight). The methylmercury concentration was measured in 6 samples of the 17, and ranged from 58% to 93% of total Hg. The concentration of total Hg is much higher than has been found in other filter feeding insects, and represents a significant potential source of Hg to fish. Mercury concentrations in Simulium spp. at different sites were strongly positively correlated with dissolved organic carbon, and the proportion of land within each catchment that was wetland. There was also a strong negative correlation with pH. By examining Hg concentration in filter feeding insects we have found a significant entry point for Hg and MeHg into the food web.     

Seasonal variation of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïd, copepod). Part 2: Alkylphenol-polyethoxylates

The occurrence and fate of alkylphenols in various matrices of the Seine River Estuary were studied. Nonylylphenols (NP) and nonylphenol polethoxylates (NPEs) were monitored in surface dissolved water, suspended particulate matter (SPM) and in a copepod, Eurytemora affinis from November 2002 to January 2004. NPs, nonylphenol mono and diethoxylates (NP1EO, NP2EO) and nonylphenol-ethoxy-acetic-acid (NP1EC) were detected and measured in all dissolved water and SPM samples whereas nonylphenoxy-acetic-acid (NP2EC) was only found sporadically in dissolved water samples. Seasonal variation of total concentrations of NPs and NPEs, ranging, respectively from 399 to 2214ngl(-1) and from 405 to 9636ngg(-1), were measured in the dissolved water and in the SPM. Significant decreases were observed in the water-column during the maximum biological activity periods in spring and autumn. Furthermore, increasing levels were observed in the SPM during the winter period. High concentrations of NP1EO and NP were detected in all copepod samples, ranging from 3423 to 6406ngg(-1). This study is the first to report high levels of endocrine disruptors in estuarine copepods.     

Changes in microbiological metabolism under chemical stress

Chemical stress may alter microbiological metabolism and this, in turn, may affect the natural and engineered systems where these organisms function. The impact of chemical stress on microbiological metabolism was investigated using model chemicals 2,4-dinitrophenol (DNP), pentachlorophenol (PCP), and N-ethylmaleimide (NEM). Biological activity of Pseudomonas aeruginosa was measured in batch systems, with and without stressors at sub-lethal concentrations. Stressor DNP, between 49 and 140 mg l(-1), and PCP, at 15 and 38 mg l(-1), caused decreases in biomass growth yields, but did not inhibit substrate utilization rates. These effects increased with stressor concentrations, showing as much as a 10% yield reduction at the highest DNP concentration. This suggests that a portion of carbon and energy resources are diverted from growth and used in stress management and protection. Stressor DNP, between 300 and 700 mg l(-1), and PCP at 85 mg l(-1) caused decreases in growth yields and substrate utilization rates. This suggests an inhibition of both anabolism and catabolism. Stressor NEM was the most potent, inhibiting biological activity at concentrations as low as 2.7 mg l(-1). These findings will ultimately be useful in better monitoring and management of biological treatment operations and contaminated natural systems.     

Effect of phosphorus addition on the reductive transformation of pentachlorophenol (PCP) and iron reduction with microorganism involvement

The transformation of phosphorus added to the soil environment has been proven to be influenced by the Fe biochemical process, which thereby may affect the transformation of organic chlorinated contaminants. However, the amount of related literatures regarding this topic is limited. This study aimed to determine the effects of phosphorus addition on pentachlorophenol (PCP) anaerobic transformation, iron reduction, and paddy soil microbial community structure. Results showed that the transformation of phosphorus, iron, and PCP were closely related to the microorganisms. Moreover, phosphorus addition significantly influenced PCP transformation and iron reduction, which promoted and inhibited these processes at low and high concentrations, respectively. Both the maximum reaction rate of PCP transformation and the maximum Fe(II) amount produced were obtained at 1 mmol/L phosphorus concentration. Among the various phosphorus species, dissolved P and NaOH-P considerably changed, whereas only slight changes were observed for the remaining phosphorus species. Microbial community structure analysis demonstrated that adding low concentration of phosphorus promoted the growth of Clostridium bowmanii, Clostridium hungatei, and Clostridium intestinale and Pseudomonas veronii. By contrast, high-concentration phosphorus inhibited growth of these microorganisms, similar to the curves of PCP transformation and iron reduction. These observations indicated that Clostridium and P. veronii, especially Clostridium, played a vital role in the transformation of related substances in the system. All these findings may serve as a reference for the complicated reactions among the multiple components of soils.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

Congener-specific intake fractions for PCDDs/DFs and Co-PCBs: modeling and validation

Intake fractions (iFs) for emissions to air, water, and soil for 17 PCDDs/DFs and 12 Co-PCBs were calculated with a level III multimedia model and a food-chain exposure model in succession. The two integrated models were tested by comparing the predicted and measured concentrations in the environment and by comparing intakes through food. Measurement-based iFs were also calculated and compared with the model-based iFs. The air concentrations predicted by the fate model were close to the median of the observed concentrations, whereas the predicted soil and water concentrations were one-third to one-tenth the observed concentrations. This difference was large in case of PCDDs and Co-PCBs, which was explained by the past pollution such as commercial PCB products and PCDD impurities in chloronitrofen (CNP) and pentachlorophenol (PCP). For fish, the predicted and observed exposures agreed well each other. For meat and milk, the predicted exposures were about 10 times the observed exposures for PCDDs/DFs, whereas the predicted and observed values agreed well for Co-PCBs. When the model was modified to consider feeding of fish meal to livestock and geographic bias in feed-grass production, the predicted congener profile was comparable to the measured profile. The comparison also suggested that chickens should be modeled separately from other terrestrial livestock. The model-based iFs for air emission of OCDD and 2378-TCDD were 0.001% and 0.1%, respectively. The iFs of most Co-PCBs were higher than those of PCDDs/DFs. These iF differences suggest the importance of the fate factor in assessing emissions of the 29 congeners.     

Reproductive success and chlorinated hydrocarbon contamination in tree swallows (Tachycineta bicolor) nesting along rivers receiving pulp and paper mill effluent discharges

The insectivorous tree swallow was chosen as an indicator species to investigate the uptake of pulp mill-related chlorinated hydrocarbons from emergent aquatic insects. Nest box populations were monitored for reproductive success at locations upstream and downstream of pulp mills on two river systems in British Columbia, Canada. Also, 16-day-old nestlings were collected and analysed for polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), pesticides, chlorophenols and chloroguaiacols. Most reproductive parameters were not different between populations at upstream and downstream locations, and were equivalent to or greater than those recorded for other tree swallow populations. Chlorinated hydrocarbon contamination of nestlings was low at all sites. The highest tissue concentrations were detected downstream of pulp mills on the Fraser River, where PCDD and PCDF patterns along with the presence of pentachlorophenol (PCP) suggested that the primary source of contaminants was past use of PCP for timber preservation. Although the absolute tissue concentration of contaminants was less, the toxic concentration (as estimated with I-TEQs) was greatest in nestlings downstream of a pulp mill on the Thompson River. The proportionately larger contributions from 2,3,7,8-TCDF and PCB-77 elevated these TEQs in comparison to other populations. Nest success was the one reproductive measure that showed substantial reductions in downstream populations on both rivers; however, there was little indication that nest failures were the direct result of contamination. Failures were largely due to parental abandonment, and, while poor parental attentiveness and nest abandonment have been associated with chlorinated hydrocarbon tissue concentrations in other studies, our 1-year assessment was insufficient to establish any link with pulp mill effluent exposure. Nestling growth models showed some subtle differences in growth patterns between nest box populations on the two rivers, but an association with pulp mill effects on aquatic insect prey availability was not established.     

Sorption of pentachlorophenol on surficial sediments: the roles of metal oxides and organic materials with co-existed copper present

The sorption characteristics of pentachlorophenol (PCP) in the surficial sediments were investigated using a selective extraction procedure. The results show that the Gamma(max) of PCP sorption decreased from 1.60mumolg(-1) to 0.69mumolg(-1) by approximately 60% after selective removal of organic materials from the sediments. The sorption of PCP in the sediments after selective removal of Mn oxides increased nearly up to 600% (from 1.60mumolg(-1) to 11.11mumolg(-1)) and, to a less degree, the PCP sorption in the sediments after simultaneous removal of Fe/Mn oxides (Gamma(max)=3.53mumolg(-1)). The analysis of the data using an additional model indicates that the contribution of Mn oxides to PCP sorption was negative, and Fe oxides and organic materials both have greater potential for sorption of PCP with less contribution from residues including Mn and Fe oxides in the residual fractions determined by a sequential extraction procedure and clay and silicate minerals. The differences in the decreased degrees of PCP sorption with increasing of Cu suggest that competition between Cu and PCP for sorption sites mainly takes place on Fe oxides.     

Sorption-desorption behavior of PCP on soil organic matter and clay minerals

Pentachlorophenol (PCP) contamination is a severe environmental problem due to its widespread occurrence, toxicity and recalcitrance. In order to gain a better understanding of the fate of PCP in soils, the role of the soil organic matter (SOM) and clay minerals in the PCP sorption-desorption was studied on two bulk field soils, two subsoils (i.e., SOM or clay-removed soil) and two artificial soils. The two field soils used were a silty loam from New Mexico (NM) containing 10% clay and a sandy-clay-loam from Colombia (CO) South America comprised of 18% clay minerals. The bulk CO soil containing kaolinite sorbed significantly less PCP than the NM soil. All soils depicted an apparent hysteresis during sorption. The CO bulk and subsoils desorbed 14-20% and 15-26% of the sorbed PCP respectively whereas the NM bulk and subsoils desorbed only 4-12% and 5-16%, respectively. Experiments conducted with pure clay and artificial soils indicated that the expandable clay minerals were key sorbent material. Additional studies to investigate the interaction between SOM and clay minerals are needed to fully understand sorptive phenomena.     

Nano-silver in drinking water and drinking water sources: stability and influences on disinfection by-product formation

Nano-silver is increasingly used in consumer products from washing machines and refrigerators to devices marketed for the disinfection of drinking water or recreational water. The nano-silver in these products may be released, ending up in surface water bodies which may be used as drinking water sources. Little information is available about the stability of the nano-silver in sources of drinking water, its fate during drinking water disinfection processes, and its interaction with disinfection agents and disinfection by-products (DBPs). This study aims to investigate the stability of nano-silver in drinking water sources and in the finished drinking water when chlorine and chloramines are used for disinfection and to observe changes in the composition of DBPs formed when nano-silver is present in the source water. A dispersion of nano-silver particles (10 nm; PVP-coated) was used to spike untreated Ottawa River water, treated Ottawa River water, organic-free water, and a groundwater at concentrations of 5 mg/L. The diluted dispersions were kept under stirred and non-stirred conditions for up to 9 months and analyzed weekly using UV absorption to assess the stability of the nano-silver particles. In a separate experiment, Ottawa River water containing nano-silver particles (at 0.1 and 1 mg/L concentration, respectively) was disinfected by adding sodium hypochlorite (a chlorinating agent) in sufficient amounts to maintain a free chlorine residual of approximately 0.4 mg/L after 24 h. The disinfected drinking water was then quenched with ascorbic acid and analyzed for 34 neutral DBPs (trihalomethanes, haloacetonitriles, haloacetaldehydes, 1,1 dichloro-2-propanone, 1,1,1 trichloro-2-propanone, chloropicrin, and cyanogen chloride). The results were compared to the profile of DBPs obtained under the same conditions in the absence of nano-silver and in the presence of an equivalent concentration of Ag⁺ ions (as AgNO₃). The stability of the nano-silver dispersions in untreated Ottawa River water, with a dissolved organic carbon concentration of 6 mg/L, was significantly higher than the stability of the nano-silver dispersions in distilled, organic-free water. Nano-silver particles suspended in the groundwater agglomerated and were quickly and quantitatively removed from the solution. Our data confirm previous observations that natural dissolved organic matter stabilizes nano-silver particles, while the high-ionic strength of groundwater appears to favor their agglomeration and precipitation. As expected, nano-silver was not stable in Ottawa River water through the chlorination process, but survived for many days when added to the Ottawa River water after treatment with chlorine or chloramines. Stirring appeared to have minimal effect on nano-silver stability in untreated and treated Ottawa River water. The profile of DBPs formed in the presence of nAg differed significantly from the profile of DBPs formed in the absence of nAg only at the 1 mg/L nAg concentration. The differences observed consisted mainly in reduced formation of some brominated DBPs and a small increase in the formation of cyanogen chloride. The reduced formation of brominated congeners may be explained by the decrease in available bromide due to the presence of Ag⁺ ions. It should be noted that a concentration of 1 mg/L is significantly higher than nAg concentrations that would be expected to be present in surface waters, but these results could be significant for the disinfection of some wastewaters with comparably high nano-silver concentrations.