Purpose Besides classical organic pollutants and pesticides, pharmaceuticals and their residues have nowadays become recognized as relevant environmental contaminants. The risks of these chemicals for aquatic ecosystems are well known, but information about the pharmaca-plant interactions and metabolic pathways is scarce. Therefore, we investigate the process of uptake of acetaminophen (N-Acetyl-4-aminophenol) by Brassica juncea, drug-induced defense responses and detoxification mechanisms in different plant parts. Material and methods Hydroponically grown Indian mustard (Brassica juncea L. Czern.) plants were treated with acetaminophen and root and leaf samples were collected after 24, 72, and 168 h of treatment. The uptake of acetaminophen and the formation of its metabolites were analyzed using LC-MS/MS technique and enzyme activities including glutathione S-transferases (GSTs) as well as several plant defense enzymes like catalase, ascorbat peroxidase, peroxidase, and glutathione reductase were assayed spectrophotometrically. Results We determined the uptake and the translocation of acetaminophen, and we tried to identify the steps of the detoxification process by assaying typical enzymes, supposing the involvement of the same- or similar enzymes and reactions as in the mammalian detoxification process. After 24-h exposure, effective uptake and translocation were observed to the upper part of plants followed by two independent conjugative detoxification pathways. Changes in antioxidant defense enzyme activities connected to the defense pathway towards reactive oxygen species indicate an additional oxidative stress response in the plants. Conclusions The major metabolic pathways in mammals are conjugation with activated sulfate and glucuronic acid, while a small amount of acetaminophen forms a chemically reactive and highly toxic, hydroxylated metabolite. We identified a glutathionyl and a glycoside conjugate, which refer to the similarities to mammalian detoxification. Increased GST activities in leaf tissues were observed correlated with the appearance of the acetaminophen-glutathione conjugate which shows the involvement of this enzyme group in the metabolism of acetaminophen in plants to organic pollutants and xenobiotics. High acetaminophen concentrations lead to oxidative stress and irreversible damages in the plants, which necessitates further investigations using lower drug concentrations for the deeper understanding of the induced detoxification—and defense processes.

Background, aim and scope Photochemical processes can decontaminate the aqueous environment from xenobiotics, but they also produce secondary pollutants. This paper presents field and laboratory evidence of the transformation of 4-chlorophenol (4CP) into 2-nitro-4-chlorophenol (2N4CP). Materials and methods Field monitoring of 4CP and 2N4CP was carried out by solid phase extraction coupled with liquid chromatography-multiple reaction monitoring mass spectrometry. Laboratory irradiation experiments were carried out under a UV-Vis lamp, and the time evolution of the compounds of interest was followed by liquid chromatography. Purpose The purpose of this study was elucidating the pathways leading to 2N4CP from 4CP in paddy field water. Results and discussion The field monitoring results suggest that 4CP can be transformed into 2N4CP in the paddy field water of the Rhône delta (Southern France). The laboratory study indicates that the transformation can take place via photonitration by •NO₂. The nitration process is inhibited by bicarbonate, possibly due to basification that favours the occurrence of the 4-chlorophenolate. The latter could consume •NO₂ without being nitrated. Photonitration in the presence of bicarbonate could account for the observed transformation in the field. Conclusions Photonitration of 4CP to 2N4CP by •NO₂ could account for the observed interconversion of the two compounds in paddy fields. The results are of concern because 2N4CP is biorecalcitrant and toxic. Recommendations and perspectives Bicarbonate can modulate the photonitration of 4CP into 2N4CP, which can be very significant in bicarbonate-poor waters.

Background, aim, and scope To stimulate the national economy, a so-called “gold week” comprising May Day and National Day has been put in force by the government, and the first golden-week holiday began on October 1, 1999. Statistical data show that about 15,000 visitors were received each day by Emperor Qin's Terra-Cotta Museum during just such a gold week period. To evaluate the effects of tourism on indoor air, airborne samples were collected by the sedimentation plate method for 5 min during the “Oct. 1” gold week period of 2006, and both composition and changes of airborne bacteria and fungi in indoor/outdoor air in the museums were investigated. Materials and methods Airborne microbes were simultaneously collected by means of gravitational sedimentation on open Petri dishes. Three parallel samples were collected at the same time each day, and samples were subsequently incubated in the lab. Microbiology media were prepared before each experiment by a professional laboratory. Concentrations were calculated and presented as average data of colony-forming units per cubic meter of air (CFU/m³). Results The results show that (1) 13 bacterial genera and eight genera of fungi were identified from indoor and outdoor air at Emperor Qin's Terra-Cotta Museum during “Oct. 1” gold week in 2006. The bacterial groups occupied 61%, the fungi groups occupied 36%, and others occupied 3% of the total number of isolated microorganism genera. (2) As for the comparison of indoor and outdoor samples, the average concentrations of fungi were higher during the afternoon (13:00) than for the morning (09:00). The average concentrations of bacteria in indoor air were higher during the afternoon (13:00) than for the morning (9:00), and in outdoor air, they were lower during the afternoon (13:00) than for the morning (9:00). (3) The average concentrations of five dominant groups of bacteria and three dominant groups of fungi were higher during the afternoon (13:00) than for the morning (9:00) in the indoor air, but the average concentrations of fungi were higher and those of bacteria were lower during the afternoon than for the morning, for outdoor air. (4) As for the comparison of indoor samples, the bacterial daily concentrations and fungal daily concentrations were higher during the afternoon (13:00) than those for the mornings (9:00) over the 10 days. For the comparison of outdoor samples, the bacterial concentration was lower, and the fungal concentrations were higher during the afternoon (13:00) than those for the morning (9:00) over the 10 days. Discussion The results also show that the numbers of airborne bacteria and fungi had a daily character in indoor air and were higher in the afternoon. The airborne microbe concentrations were found to be similar to residential indoor values from other reports; the indoor museum maximum of microbial concentrations was 90 CFU/m³ and did not exceed the Chinese indoor bioaerosol guideline. However, microorganisms may fall on the surface of display items as a result of particle sedimentation and would, as such, be capable of degrading objects by way of their secretions, e.g., enzymes and organic acids. Therefore, the right steps should be taken to prevent any deterioration in the quality of displayed artifacts. Conclusions The results show that museum air was affected by human activity; therefore, it is imperative that the number of visitors be strictly limited and that windows be opened regularly to avoid air pollution. Recommendations and perspectives The data provide a significant scientific basis for indoor air quality control and museum scientific management. It is recommended that the number of visitors be strictly limited.

Background Chlorobenzoic acids (CBA) are intermediate products of the aerobic microbial degradation of PCB and several pesticides. This study explores the feasibility of using basket willows, Salix viminalis, to remove 4-CBA from polluted sites, which also might stimulate PCB degradation. Methods The removal of 4-CBA by willow trees was investigated with intact, septic willow trees growing in hydroponic solution and with sterile cell suspensions at concentrations of 5 mg/L and 50 mg/L 4-CBA. Nutrient solutions with different levels of ammonium and nitrate were prepared to achieve different pH levels. The concentration of 4-CBA was tracked over time and quantified by HPLC. Results and discussion At the low level of 4-CBA (5 mg/L), willows removed 70% (pH 4.2) to 90% (pH 6.8), while 48% (pH 4.2) to 52% (pH 6.8) of the water was transpired. At the high 4-CBA level (50 mg/L), the pH varied between 4.4 and 4.6, and 10% to 30% of 4-CBA was removed, but only 5% to 9% of the water. In sterile cell suspensions, removal of 4-CBA by fresh biomass was much higher than removal by dead biomass. Conclusions The results indicate that 4-CBA is toxic to willow trees at 50 mg/L. The removal of 4-CBA from solution is by both passive processes (uptake with water, sorption to plant tissue) and metabolic processes of the plants. Recommendations and outlook Plants, such as willow trees, might assist in the degradation of PCB and their degradation products CBA.

Background, aim, and scope Primitive wax refining techniques had resulted in almost 50,000 tonnes of acidic oily sludge (pH 1-3) being accumulated inside the Digboi refinery premises in Assam state, northeast India. A novel yeast species Candida digboiensis TERI ASN6 was obtained that could degrade the acidic petroleum hydrocarbons at pH 3 under laboratory conditions. The aim of this study was to evaluate the degradation potential of this strain under laboratory and field conditions. Materials and methods The ability of TERI ASN6 to degrade the hydrocarbons found in the acidic oily sludge was established by gravimetry and gas chromatography-mass spectroscopy. Following this, a feasibility study was done, on site, to study various treatments for the remediation of the acidic sludge. Among the treatments, the application of C. digboiensis TERI ASN6 with nutrients showed the highest degradation of the acidic oily sludge. This treatment was then selected for the full-scale bioremediation study conducted on site, inside the refinery premises. Results The novel yeast strain TERI ASN6 could degrade 40 mg of eicosane in 50 ml of minimal salts medium in 10 days and 72% of heneicosane in 192 h at pH 3. The degradation of alkanes yielded monocarboxylic acid intermediates while the polycyclic aromatic hydrocarbon pyrene found in the acidic oily sludge yielded the oxygenated intermediate pyrenol. In the feasibility study, the application of TERI ASN6 with nutrients showed a reduction of solvent extractable total petroleum hydrocarbon (TPH) from 160 to 28.81 g kg⁻¹ soil as compared to a TPH reduction from 183.85 to 151.10 g kg⁻¹ soil in the untreated control in 135 days. The full-scale bioremediation study in a 3,280-m² area in the refinery showed a reduction of TPH from 184.06 to 7.96 g kg⁻¹ soil in 175 days. Discussion Degradation of petroleum hydrocarbons by microbes is a well-known phenomenon, but most microbes are unable to withstand the low pH conditions found in Digboi refinery. The strain C. digboiensis could efficiently degrade the acidic oily sludge on site because of its robust nature, probably acquired by prolonged exposure to the contaminants. Conclusions This study establishes the potential of novel yeast strain to bioremediate hydrocarbons at low pH under field conditions. Recommendations and perspectives Acidic oily sludge is a potential environmental hazard. The components of the oily sludge are toxic and carcinogenic, and the acidity of the sludge further increases this problem. These results establish that the novel yeast strain C. digboiensis was able to degrade hydrocarbons at low pH and can therefore be used for bioremediating soils that have been contaminated by acidic hydrocarbon wastes generated by other methods as well.

Background, aim, and scope Acrylate and methacrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon (CH₂=CHCOO- and CH₂=CCH₃COO-, respectively) and are widely used in the polymer plastic and resin production. Rate coefficients for Cl reactions for most of the unsaturated esters have not been previously determined, and a good understanding is needed of all the atmospheric oxidation processes of these compounds in order to determine lifetimes in the atmosphere and to evaluate the impact of these reactions on the formation of photo-oxidants and therefore on health and environment. Materials and methods The relative rate technique has been used to obtain rate coefficients for the reactions between the Cl atom and a series of unsaturated esters. The experiments have been carried out in a static Teflon reactor at room temperature and atmospheric pressure (N₂ as bath gas) using gas chromatography with flame ionization detection as detection system. Results The following rate coefficients are obtained (in cubic meter per molecule per second): methyl acrylate + Cl = 1.71 ± 0.13 × 10⁻¹⁰; methyl methacrylate + Cl = 2.30 ± 0.18 × 10⁻¹⁰; ethyl acrylate + Cl = 1.82 ± 0.13 × 10⁻¹⁰; ethyl methacrylate + Cl = 2.71 ± 0.21 × 10⁻¹⁰; butyl acrylate + Cl = 2.94 ± 0.23 × 10⁻¹⁰; butyl methacrylate + Cl = 3.83 ± 0.30 × 10⁻¹⁰; methyl 3-methyl acrylate + Cl = 2.21 ± 0.17 × 10⁻¹⁰; and methyl 3,3-dimethyl acrylate + Cl = 3.58 ± 0.28 × 10⁻¹⁰. Discussion Rate coefficients calculated for Cl reactions are around one order of magnitude higher than OH ones. The effect in the reactivity of increased substitution at the carbon-carbon double bond is analyzed and also the effect of the identity of the alkyl group R in the -C(O)OR. Atmospheric lifetimes of the compounds against the attack by the major oxidants are estimated and the atmospheric implications are discussed. Conclusions The dominant atmospheric loss process for acrylate esters is clearly their daytime reaction with the hydroxyl radical. However, in coastal areas and in the marine boundary layer and in some industrial zones, Cl-atom-initiated degradation of the unsaturated esters considered here can be a significant if not dominant homogeneous loss process. Recommendations and perspectives Product analysis should be necessary in order to evaluate the real environmental impact of these reactions. OH and ozone reactions of most of the considered compounds have already been studied and products determined, but kinetic and products information for NO₃ radical reactions is especially scarce.

Introduction In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO₂ photocatalysis at pH 4 and 9, and the formation of degradation intermediates and final products under specific experimental conditions. Experimental observations and theoretical considerations allowed us to suggest the degradation mechanism of DDVP by the UV/TiO₂ process in aqueous solution. Methods The irradiation experiments were carried out in a photoreactor using a 228-W medium-pressure Hg vapor lamp. The concentration of DDVP, phosphate ion and formaldehyde as reaction intermediate, are determined spectrophotometrically. Chloride ion concentration was measured potentiometrically. Results The photocatalytic degradation rate of dichlorvos (DDVP) under UV irradiation (360-380 nm) was optimized with respect to the flow rate of O₂ gas sparged into the solution and photocatalyst concentration for a constant dichlorvos concentration (1.66×10⁻⁴ M) at pH 4. Kinetic data were obtained at pH 4 and pH 9 for dichlorvos and the inorganic species released through its photo-induced degradation. The proposed mechanism which assumes the formation of some toxic intermediates resistant to mineralization is supported by theoretical calculations and the observed inorganic mass balances. Conclusions The calculated pseudo-first-order rate constants were dependent on the dissolved oxygen level at low O₂ flow rate, but somewhat independent on the initial pH. The decrease of pH during the irradiation suggests the formation of organic acids. The presence of organic intermediates was confirmed also by TOC measurements. A plausible reaction mechanism of DDVP degradation through the UV-A/TiO₂ process was proposed.

Background, aim, and scope Experimental data on partition coefficients and environmental half-lives of sulfur analogs of polychlorinated organic compounds are scarce. Consequently, little is known about their overall persistence and long-range transport potential, which are the most vital measures in the environmental exposure assessment. We performed Multimedia Modeling of environmental fate and transport to complement this paucity of scientific data. The main aim of our study was to investigate whether the sulfur analogs of polychlorinated dibenzo-p-dioxins, -dibenzofurans, and -diphenylethers are as environmentally persistent and/or mobile as their oxygen counterparts and to propose the environmental exposure-related classification of the examined sulfur compounds. Materials and methods Our study included all possible congeners of the sulfur analogs generated in a combinatorial approach. We predicted (1) lacking data on partition coefficients (log K OW, log K OA and log K AW) for oxygen- and sulfur analogs using Quantitative Structure-Property Relationship (QSPR) modeling and (2) their half-lives in air, water, and soil using US EPA tool ‘The PBT Profiler, v. 1.203 2006'. Subsequently, we introduced these results into multimedia mass balance model ‘The OECD POV and LRTP Screening Tool, v. 2.2'. Results Our study revealed that log K OW and log K OA are increasing by constant values of 0.60 and 1.07, respectively, and the values of log K AW are decreasing by 0.90, whenever one oxygen atom in the carbon skeleton is replaced by sulfur. The persistence ranking performed by the PBT Profiler showed that PCDDs, PCDFs, PCDEs, and their sulfur analogs belong to one half-life class. Discussion The Multimedia Modeling by the means of ‘The OECD POV and LRTP Screening Tool, v. 2.2' suggested that the long-range transport potential depends on the presence/absence of oxygen/sulfur atoms in particular molecules, their substitution pattern and the parent carbon skeleton. Sulfur analogs are generally less mobile than their oxygen analogs, but have similar overall persistence and much higher bioaccumulation potential. Thus, according to the classification of chemicals proposed by Klasmeier et al. (Environ Sci Technol 40:53-60, 2006), some of them show POP-like POV and LRTP characteristics while the rest shows POP-like POV characteristics. Conclusions The sulfur analogs of PCDDs, PCDFs, or PCDEs bring environmental mobility comparable with the risk related to the oxygen ones; they belong to the pollutants of ‘highest' or ‘intermediate' priority. Recommendations and perspectives Further studies that would verify the necessity to include the studied sulfur molecules in the international lists of high-priority environmental pollutants are recommended.

Background, aim, and scope This review deals with publications concerning the mode of action of Bt proteins and their potential synergism with extrinsic factors. The aim was to assess the impact of those factors especially regarding selectivity and efficacy of Bt toxins and to discuss possible gaps in current risk assessment of genetically engineered plants expressing Bt toxins. Main features The review shows that several extrinsic factors are able to influence the selectivity and efficacy of Bt toxins. The findings are seen as being relevant for risk assessment in Bt plants. This conclusion is derived by discussing current state of knowledge about the mode of action of Bt proteins, unexpected effects on non-target organism, and the way how modified Bt toxins are expressed in genetically engineered plants. Results Several publications have been identified that show that certain factors and synergism can impact efficacy and selectivity of Bt toxins. These extrinsic factors are various and include other Bt toxins or parts from the spore of Bacillus thuringiensis as well as certain enzymes, environmental stress, non-pathogenic microorganisms, and infectious diseases. Discussion Research on the underlying mechanism of observed synergism might help to explain some of the effects found in non-target organisms. In general, possible synergism of Bt toxins with extrinsic factors can be relevant for risk assessment of genetically engineered Bt plants since they expose a modified Bt toxin to the environment under various conditions and over a long period of time. Conclusions Risk assessment of genetically engineered plants should put into question the general assumption of a high selectivity and a linear dose-response relationship in the toxicity of Bt proteins. Both selectivity and efficacy can be influenced by synergism, which can provoke unexpected and undesired effects in non-target organisms. Perspectives It is suggested that systematic research be promoted on synergism between Bt toxins and potential extrinsic factors that could impact the spectrum of susceptible organisms. This research should become a prerequisite for risk assessment of Bt plants.

Purpose Experiments were conducted to examine the effects of mercury (Hg) on soil nitrification activities and the microbial communities of ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA). Methods The soil samples spiked with different Hg concentrations were incubated for a period of 1, 2, 4, and 8 weeks in triplicate and the potential nitrification rate (PNR) of the samples was determined. The abundance of AOB and AOA was measured after an 8-week incubation by real-time polymerase chain reaction (PCR) assay of the amoA genes, while the community compositions by cloning and sequencing approaches. Results The soil PNR differed with different incubation periods. It tended to decrease with increasing soil Hg concentrations at week 1, basing on which the half-maximal effective concentration (EC50) was 1.59 mg kg⁻¹. There was no significant difference in the abundance of AOB or AOA among the treatments. The AOB community was dominated by Nitrosospira-like sequences and more than 70% of the obtained clones were affiliated with the cluster 3a.2. The percentage of cluster 3a.1 in AOB community appeared to a consistent trend of decreasing with ascending soil Hg concentrations. While all the AOA sequences in the clone libraries were grouped into cluster S (soil and sediment origin). Conclusions This study revealed that Hg could inhibit soil potential nitrification and the extent varied with incubation periods. Soil Hg pollution changed the composition of soil AOB to some extent. These findings will be helpful to recognize the effects of Hg on the activity and community composition of soil ammonia oxidizers.