Investigation of triclosan fate and toxicity in continuous-flow activated sludge systems

The purpose of this research was to study the fate and toxicity of triclosan (TCS) in activated sludge systems and to investigate the role of biodegradation and sorption on its removal. Two continuous-flow activated sludge systems were used; one system was used as a control, while the other received TCS concentrations equal to 0.5 and 2mgl(-1). At the end of the experiment, 1mgl(-1) TCS was added in the control system to investigate TCS behaviour and effects on non-acclimatized biomass. For all concentrations tested, more than 90% of the added TCS was removed during the activated sludge process. Determination of TCS in the dissolved and particulate phase and calculation of its mass flux revealed that TCS was mainly biodegraded. Activated sludge ability to biodegrade TCS depended on biomass acclimatization and resulted in a mean biodegradation of 97%. Experiments with batch and continuous-flow systems revealed that TCS is rapidly sorbed on the suspended solids and afterwards, direct biodegradation of sorbed TCS is performed. Regarding TCS effects on activated sludge process, addition of 0.5mgl(-1) TCS on non-acclimatized biomass initially deteriorated ammonia removal and nitrification capacity. After acclimatization of biomass, nitrification was fully recovered and further increase of TCS to 2mgl(-1) did not affect the performance of activated sludge system. The effect of TCS on organic substrate removal was minor for concentrations up to 2mgl(-1), indicating that heterotrophic microorganisms are less sensitive to TCS than nitrifiers.     

Repeated batch and continuous degradation of chlorpyrifos by Pseudomonas putida

The present study was undertaken with the objective of studying repeated batch and continuous degradation of chlorpyrifos (O,O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) using Ca-alginate immobilized cells of Pseudomonas putida isolated from an agricultural soil, and to study the genes and enzymes involved in degradation. The study was carried out to reduce the toxicity of chlorpyrifos by degrading it to less toxic metabolites. Long-term stability of pesticide degradation was studied during repeated batch degradation of chlorpyrifos, which was carried out over a period of 50 days. Immobilized cells were able to show 65% degradation of chlorpyrifos at the end of the 50th cycle with a cell leakage of 112 × 10³ cfu mL^?1. During continuous treatment, 100% degradation was observed at 100 mL h^?1 flow rate with 2% chlorpyrifos, and with 10% concentration of chlorpyrifos 98% and 80% degradation was recorded at 20 mL h^?1 and 100 mL h^?1 flow rate respectively. The products of degradation detected by liquid chromatography–mass spectrometry analysis were 3,5,6-trichloro-2-pyridinol and chlorpyrifos oxon. Plasmid curing experiments with ethidium bromide indicated that genes responsible for the degradation of chlorpyrifos are present on the chromosome and not on the plasmid. The results of Polymerase chain reaction indicate that a ~890-bp product expected for mpd gene was present in Ps. putida. Enzymatic degradation studies indicated that the enzymes involved in the degradation of chlorpyrifos are membrane-bound. The study indicates that immobilized cells of Ps. putida have the potential to be used in bioremediation of water contaminated with chlorpyrifos.     

Partitioning of arsenic in soil-crop systems irrigated using groundwater: a case study of rice paddy soils in southwestern Taiwan

The accumulation of As in rice due to groundwater irrigation in paddy fields represents a serious health hazard in South and Southeast Asia. In Taiwan, the fate of As in long-term irrigated paddy fields is poorly understood. Groundwater, surface soil, and rice samples were collected from a paddy field that was irrigated with As-containing groundwater in southwestern Taiwan. The purpose of this study is to elucidate the source and sink of As in the paddy field by comparing the As fractions in the soils that were obtained by a sequential extraction procedure (SEP) with the As uptake of rice. The risks associated with eating rice from the field can thus be better understood. The concentration of As in groundwater varied with time throughout the growing seasons of rice, but always exceeded the permitted maximum (10 μg L⁻¹) for drinking water by the WHO. The As concentration increased with the concentration of Fe in the groundwater, supporting the claim that a large amount of As was concentrated in the Fe flocs collected from the internal wall of the groundwater pump. The results of the SEP revealed that As bound with amorphous and crystalline hydrous oxides exhibited high availability in the soils. The root of rice accumulated the largest amount of As, followed by the straw, husk, and grain. Although the As concentration in the rice grain was less than 1.0 mg kg⁻¹, the estimated intake level was close to the maximum tolerable daily intake of As, as specified by the WHO.     

Modeling the formation and fate of odorous substances in collection systems.

A conceptual model that simulates the formation and fate of odorous substances in branched collection systems is presented. The model predicts the activity of the relevant biomass phenotypes under aerobic, anoxic, and anaerobic conditions in force mains and gravity sewers. The formation and fate of individual, malodorous substances in the bulk water, biofilms, and sediments are modeled. The release of odorous compounds from the bulk water to the sewer gas phase, their fate in the gas phase, and their subsequent release into the urban atmosphere is simulated. Examples of model application include the prediction of hydrogen sulfide and malodorous fermentation products from force mains and gravity sewers.     

Long-term fate of exogenous metals in a sandy Luvisol subjected to intensive irrigation with raw wastewater

From 1899 to 2002, sandy Luvisol in the Paris region has been intensively irrigated with raw wastewater, resulting in major soil pollution by metallic trace elements (MTE). To identify the soil phases implicated in retaining these metals, sequential extractions were performed on a solum irrigated with untreated wastewater and another reference solum. The endogenous and exogenous fractions of MTE in the contaminated soil were discriminated using correlations between MTE and major elements defined from unpolluted soils of the area. In the contaminated soil no exogenous lead and chromium are present below the surface horizon, whereas exogenous zinc and copper are found down to the base of the solum. The endogenous MTE are mainly found in the residual fraction. Exogenous MTE appear to be associated with organic matter in the surface horizon, and exogenous zinc seems to be readsorbed on iron and manganese oxyhydroxides in the underlying horizons.     

Modelling the geochemical fate and transport of wastewater-derived phosphorus in contrasting groundwater systems

A 1D reactive transport model (RTM) is used to obtain a mechanistic understanding of the fate of phosphorus (P) in the saturated zone of two contrasting aquifer systems. We use the field data from two oxic, electron donor-poor, wastewater-impacted, sandy Canadian aquifers, (Cambridge and Muskoka sites) as an example of a calcareous and non-calcareous groundwater system, respectively, to validate our reaction network. After approximately 10 years of wastewater infiltration, P is effectively attenuated within the first 10 m down-gradient of the source mainly through fast sorption onto calcite and Fe oxides. Slow, kinetic sorption contributes further to P removal, while precipitation of phosphate minerals (strengite, hydroxyapatite) is quantitatively unimportant in the saturated zone. Nitrogen (N) dynamics are also considered, but nitrate behaves essentially as a conservative tracer in both systems. The model-predicted advancement of the P plume upon continued wastewater discharge at the calcareous site is in line with field observations. Model results suggest that, upon removal of the wastewater source, the P plume at both sites will persist for at least 20 years, owing to desorption of P from aquifer solids and the slow rate of P mineral precipitation. Sensitivity analyses for the non-calcareous scenario (Muskoka) illustrate the importance of the sorption capacity of the aquifer solids for P in modulating groundwater N:P ratios in oxic groundwater. The model simulations predict the breakthrough of groundwater with high P concentrations and low N:P ratios after 17 years at 20 m from the source for an aquifer with low sorption capacity (<0.02% w/w Fe(OH)(3)). In this type of system, denitrification plays a minor role in lowering the N:P ratios because it is limited by the availability of labile dissolved organic matter.     

Behavior of pyrimethanil,pyraclostrobin, boscalid,cypermethrin and chlorpyrifos residues on raspberry fruit and leaves of Laszka variety

The purpose of the research conducted was to investigate and evaluate the behavior of pyrimethanil, pyraclostrobin, boscalid, cypermethrin and chlorpyrifos, the active ingredients of selected fungicides and insecticides, on ripe fruit and in fully developed leaves of raspberry of the Laszka variety. The field trial was carried out in the period of one month starting from the first fruit picking. The results obtained indicated that residue levels on the day of the first crop picking did not even approximate the corresponding EU-MRLs (http://ec.europa.eu/sanco_pesticides). Individual substances in raspberry fruits and leaves disappeared at a similar rate. As a result of chlorpyrifos application to the soil, its residue in fruits and leaves occurred for the whole period of fruit bearing, though in fruit they dropped successively. To produce raspberries with residues below or equal to 0.01 μg g^?1, the application of pesticides should be stopped at least 2–3 weeks before the first crop picking, and on condition that an appropriate preparation (active in low doses) is applied to the last treatments.     

Simultaneous biodegradation of bifenthrin and chlorpyrifos by Pseudomonas sp. CB2

The degradation of bifenthrin (BF) and chlorpyrifos (CP), either together or individually, by a bacterial strain (CB2) isolated from activated sludge was investigated. Strain CB2 was identified as belonging to genus Pseudomonas based on the morphological, physiological, and biochemical characteristics and a homological analysis of the 16S rDNA sequence. Strain CB2 has the potential to degrade BF and CP, either individually or in a mixture. The optimum conditions for mixture degradation were as follows: OD_600nm = 0.5; incubation temperature = 30°C; pH = 7.0; BF-CP mixture (10 mg L^?1 of each). Under these optimal conditions, the degradation rate constants (and half-lives) were 0.4308 d^?1 (1.61 d) and 0.3377 d^?1 (2.05 d) for individual BF and CP samples, respectively, and 0.3463 d^?1 (2.00 d) and 0.2931 d^?1 (2.36 d) for the BF-CP mixture. Major metabolites of BF and CP were 2-methyl-3-biphenylyl methanol and 3,5,6-trichloro-2-pyridinol, respectively. No metabolite bioaccumulation was observed. The ability of CB2 to efficiently degrade BF and CP, particularly in a mixture, may be useful in bioremediation efforts.     

漆酶/香草醛体系生物降解毒死蜱影响因素的研究

研究了漆酶介体体系对有机磷农药毒死蜱生物降解的效果及影响因素.通过对6种介体的试验比较,筛选了合适的介体.在试验条件下,1-羟基苯并三唑(HBT)和2,2’-联氮-二(3-乙基-苯并噻唑-6-磺酸)(ABTS)对漆酶降解毒死蜱存在一定的抑制作用,紫脲酸(VA)和2,6-二甲氧基苯酚(2,6-DMP)对漆酶降解毒死蜱未起促进作用,而天然产物香草醛和愈创木酚可促进漆酶降解毒死蜱,香草醛的促进作用最为明显,选择香草醛作为漆酶介体体系中的介体.研究了漆酶/香草醛体系中,反应时间、漆酶初始酶活、pH、温度、介体投加量及投加方式、毒死蜱初始浓度等因素对毒死蜱生物降解效果的影响.结果表明,控制漆酶初始酶活为0.050 U/mL、pH为5.0、温度30℃,分2次投加香草醛(香草醛与毒死蜱初始值摩尔比分别为40和80)情况下,漆酶/香草醛体系即可在24 h内实现对25 mg/L毒死蜱的有效降解,降解率达98％.     

Application of smart irrigation systems for water conservation in Italian farms

Environmental Science and Pollution Research - In many countries, water supplies are limited and must be managed for different uses. Providing additional resources for irrigation can be an...     

Adsorption of chlorpyrifos,penconazole and metalaxyl from aqueous solution by modified clays

Sorption of three pesticides (chlorpyrifos, metalaxyl and penconazole) has been measured on a commercial clay montmorillonite and on the same mineral modified with either of two cationic-surfactant micelles. Both micelle–clay complexes, commercial names Cloisite 20A and Cloisite 30B, showed a good capacity to sorb all three pesticides from water, whereas their sorption on the natural montmorillonite was not described by an isotherm. Modelling sorption on both micelle–clay complexes showed that the Freundlich sorption constant (K _F) was higher for chlorpyrifos on Cloisite 20A (K _F = 7.76) than on Cloisite 30B (K _F = 5.91), whereas the sorption of metalaxyl was stronger on Cloisite 30B (K _F = 1.07) than on Cloisite 20A (K _F = 0.57). Moreover the micelle–clay complex Cloisite 20A also showed a good affinity for penconazole, the maximum quantity adsorbed (q _m) of 6.33 mg g^?1 being 45% more than that on Cloisite 30B. Single-batch adsorption of each pesticide onto both micelle–clay complexes was studied using the Freundlich isotherm for chlorpyrifos and metalaxyl and the Langmuir isotherm for penconazole. The Cloisite 20A micelle–clay complex was predicted to require 23% less adsorbent to treat certain volumes of wastewater containing 30 mg L^?1 chlorpyrifos, 43% more to treat metalaxyl similarly and 57% less to treat penconazole compared with Cloisite 30B.     

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag–Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag–PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72 h in freshwater (500–600 μg L⁻¹) and seawater (1300–1500 μg L⁻¹), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag⁺ (1.1, 400 and 0.11 μg L⁻¹, respectively), Ag–Cit (3.0, 2380 and 0.15 μg L⁻¹, respectively) and Ag–PVP (19.5, 3690 and 2.0 μg L⁻¹, respectively) varied widely, with toxicity in the order Ag⁺ > Ag–Cit > Ag–PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag⁺ or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.     

Behavior of parathion in tomatoes processed into juice and ketchup

Fresh tomatoes were cut, fortified with 25 ppm (micrograms/g) of parathion (0,0-diethyl 0-4-nitrophenylphosphorothioate) and processed into either juice or ketchup. Tomato juice was canned, while ketchup was placed in bottles. All samples were stored at room temperature for analysis at two-monthly intervals. Parathion residues were measured quantitatively by GLC, while the two metabolites, aminoparathion (0,0-diethyl 0-4-aminophenylphosphorothioate) and 4-nitrophenol, were determined colorimetrically. The presence of the three compounds was confirmed qualitatively by TLC. Blanching of tomatoes resulted in about 50% reduction of parathion level. Pulping of fruits caused a further decrease in parathion residues in juice as a result of its sorption and concentration in the semi-solid pulp. About 85% of parathion added to tomatoes was lost during the processing steps. Storage of juice resulted in a gradual decrease in parathion levels, whereby only 1.7% of the original amount was detected after six months of storage. The compound was stable in ketchup for the first four months of storage but decreased thereafter to almost 7% of the original quantity added to fruits. Aminoparathion and 4-nitrophenol were detected in low levels.     

Binding and detoxification of chlorpyrifos by lactic acid bacteria on rice straw silage fermentation

This investigation examined the reduction of pesticide residues on straw inoculated with lactic acid bacteria (LAB) during ensiling. Lactobacillus casei WYS3 was isolated from rice straw that contained pesticide residues. Non-sterilized rice straw, which was inoculated with L. casei WYS3, showed increased removal of chlorpyrifos after ensiling, compared with rice straw that was not inoculated with L. casei WYS3 or sterilized rice straw. In pure culture, these strains can bind chlorpyrifos as indicated by high-performance liquid chromatography analysis. Viable L. casei WYS3 was shown to bind 33.3–42% of exogenously added chlorpyrifos. These results are similar to those of acid-treated cells but less than those of heat-treated cells, which were found to bind 32.0% and 77.2% of the added chlorpyrifos respectively. Furthermore, gas chromatography–mass spectrometry analysis determined that L. casei WYS3 detoxified chlorpyrifos via P-O-C cleavage. Real-time polymerized chain reaction analysis determined that organophosphorus hydrolase gene expression tripled after the addition of chlorpyrifos to LAB cultures, compared with the control group (without chlorpyrifos). This paper highlights the potential use of LAB starter cultures for the detoxification and removal of chlorpyrifos residues in the environment.     

Diphenyl diselenide attenuates hepatic and hematologic toxicity induced by chlorpyrifos acute exposure in rats

Purpose

In this study, we investigated the effect of diphenyl diselenide [(PhSe)₂] on chlorpyrifos (CPF)-induced hepatic and hematologic toxicity in rats.

Methods

Rats were pre-treated with (PhSe)₂ (5?mg/kg) via the oral route (oral gavage) once a day for 7?days. On the eighth and ninth days, rats were treated with (PhSe)₂ (5?mg/kg) 30?min prior to CPF (50?mg/kg, by subcutaneous route). The aspartate aminotransferase, alanine aminotransferase, and lactate dehydrogenase activities were determined in plasma of rats. Lipid peroxidation, protein carbonyl, and non-protein thiol levels as well as catalase, superoxide dismutase, glutathione peroxidase, glutathione reductase, and gluthatione S-transferase activities were determined in livers of rats. Hematological parameters were also determined.

Results

The results showed that CPF caused hepatic oxidative damage, as demonstrated by an increase in lipid peroxidation and protein carbonyl levels which was associated with a decrease in antioxidant defenses. CPF exposure caused a reduction in the leukocyte, indicating hematologic toxicity. (PhSe)₂ was effective in attenuating these toxic effects caused by CPF exposure in rats.

Conclusions

The results indicated that (PhSe)₂ was effective in protecting the hepatic and hematologic toxicity induced by acute CPF exposure in rats.     

In-residence,multiple route exposures to chlorpyrifos and diazinon estimated by indirect method models

One of the objectives of the National Human Exposure Assessment Survey (NHEXAS) is to estimate exposures to several pollutants in multiple media and determine their distributions for the population of Arizona. This paper presents modeling methods used to estimate exposure distributions of chlorpyrifos and diazinon in the residential microenvironment using the database generated in Arizona (NHEXAS-AZ). A four-stage probability sampling design was used for sample selection. Exposures to pesticides were estimated using the indirect method of exposure calculation by combining measured concentrations of the two pesticides in multiple media with questionnaire information such as time subjects spent indoors, dietary and non-dietary items they consumed, and areas they touched. Most distributions of in-residence exposure to chlorpyrifos and diazinon were log-normal or nearly log-normal. Exposures to chlorpyrifos and diazinon vary by pesticide and route as well as by various demographic characteristics of the subjects. Comparisons of exposure to pesticides were investigated among subgroups of demographic categories, including gender, age, minority status, education, family income, household dwelling type, year the dwelling was built, pesticide use, and carpeted areas within dwellings. Residents with large carpeted areas within their dwellings have higher exposures to both pesticides for all routes than those in less carpet-covered areas. Depending on the route, several other determinants of exposure to pesticides were identified, but a clear pattern could not be established regarding the exposure differences between several subpopulation groups.     

The fate of methoxychlor in soils and transformation by soil microorganisms

Abstract

Methoxychlor was found to be sufficiently persistant in soil and its residues were present even 18 months after the soil treatment. Saprophytes, fungi and actinomyces were unaffected by varying concentrations of methoxychlor, azotobacter however was susceptable. Soil strains isolated did not utilize methoxychlor as a sole carbon source except for 9 cultures belonging to the genera Bacillus, Acineto‐bacter and Rhodococcus which carried out the complete dechlorination, demethylation and splitting of one of methoxychlor aromatic rings. Anaerobic conditions were more favorable for methoxychlor biodegradation by soil and pure microbial cultures.     

The fate of methoxychlor in soils and transformation by soil microorganisms

Methoxychlor was found to be sufficiently persistent in soil and its residues were present even 18 months after the soil treatment. Saprophytes, fungi and actinomyces were unaffected by varying concentrations of methoxychlor, azotobacter however was susceptable. Soil strains isolated did not utilize methoxychlor as a sole carbon source except for 9 cultures belonging to the genera Bacillus, Acinetobacter and Rhodococcus which carried out the complete dechlorination, demethylation and splitting of one of methoxychlor aromatic rings. Anaerobic conditions were more favorable for methoxychlor biodegradation by soil and pure microbial cultures.     

Conductive-diamond electrochemical oxidation of chlorpyrifos in wastewater and identification of its main degradation products by LC-TOFMS

The electrochemical transformation of the organophosphorous insecticide chlorpyrifos (CPF) was investigated in wastewater. The oxidation of CPF was carried out in a single-compartment electrochemical flow cell working under batch operation mode, using diamond-based material as anode and stainless steel as cathode. In order to evaluate its persistence and degradation pathway, two different concentration levels (1.0 mg L⁻¹ and 0.1 mg L⁻¹) were studied. Liquid chromatography/mass spectrometry was used for evaluation of the initial and electrolyzed solutions. The identification of CPF transformation products was performed by liquid chromatography-time of flight-mass spectrometry (LC-TOFMS). Results showed that CPF is completely removed at the end of treatment time. Analysis by LC-TOFMS allowed the identification of six degradation products (with Mw 154, 170, 197, 305 321 and 333). Three of the identified intermediates (Mw 170, 305 and 321) were completely removed at the end of electrolysis time. Interestingly, the formation of diethyl 3,5,6-trichloropyridin-2yl phosphate (chlorpyrifos oxon) and 3,5,6-trichloropyridin-2-ol was also found in previous reported degradation pathways using different degradation technologies.