Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

Air quality assessment by tree bark biomonitoring in urban, industrial and rural environments of the Rhine Valley: PCDD/Fs, PCBs and trace metal evidence

Tree barks were used as biomonitors to evaluate past atmospheric pollution within and around the industrial zones of Strasbourg (France) and Kehl (Germany) in the Rhine Valley. The here estimated residence time for trace metals, PCBs and PCDD/Fs in tree bark is >10 years. Thus, all pollution observed by tree bark biomonitoring can be older than 10 years. The PCB baseline concentration (sum of seven PCB indicators (Σ₇PCB_ind)) determined on tree barks from a remote area in the Vosges mountains is 4 ng g⁻¹ and corresponds to 0.36 × 10⁻³ ng toxic equivalent (TEQ) g⁻¹ for the dioxin-like PCBs (DL-PCBs). The northern Rhine harbor suffered especially from steel plant, waste incinerator and thermal power plant emissions. The polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations analyzed in tree barks from this industrial area range between 392 and 1420 ng kg⁻¹ dry-weight (dw) corresponding to 3.9 ng TEQ_PCDD/Fs kg⁻¹ to 17.8 ng TEQ_PCDD/Fs kg⁻¹, respectively. Highest PCDD/F values of 7.2 ng TEQ kg⁻¹ to 17.8 ng TEQ kg⁻¹ have been observed close to and at a distance of <2 km southwest of the chemical waste incinerator. However, very close to this incinerator lowest TEQ dioxin-like PCB (TEQ_DL-PCB) values of 0.006 ng TEQ g⁻¹ have been found. On the other hand close to and southwest and northeast of the steel plant the values are comparatively higher and range between 0.011 ng TEQ g⁻¹ and 0.026 ng TEQ g⁻¹. However, even stronger Σ₇PCB_ind enrichments have been observed at a few places in the city center of Kehl, where ΣDL-PCB values of up to 0.11 ng TEQ g⁻¹ have been detected. These enrichments, however, are the result of ancient pollutions since recent long-term measurements at the same sites indicate that the atmospheric PCB concentrations are close to baseline. Emissions from an old landfill of waste and/or great fires might have been the reasons of these PCB enrichments. Other urban environments of the cities of Kehl and Strasbourg show significantly lower Σ₇PCB_ind concentrations. They suffer especially from road and river traffic and have typically Σ₇PCB_ind concentrations ranging from 11 ng g⁻¹ to 29 ng g⁻¹. The PCB concentration of 29 ng g⁻¹ has been found in tree bark close to the railway station of Strasbourg. Nevertheless, the corresponding TEQ_DL-PCB are low and range between 0.2 × 10⁻³ ng TEQ g⁻¹ and 7 × 10⁻³ ng TEQ g⁻¹. Samples collected near road traffic are enriched in Fe, Sb, Sn and Pb. Cd enrichments were found close to almost all types of industries. Rural environments not far from industrial sites suffered from organic and inorganic pollution. In this case, TEQ_DL-PCB values may reach up to 58 × 10⁻³ ng TEQ g⁻¹ and the corresponding V, Cr, Co, Ni, and Cd concentrations are comparatively high.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Hydroxytyrosol, the phenolic compound of olive oil protects human PBMC against oxidative stress and DNA damage mediated by 2,3,7,8-TCDD

The protective effect of hydroxytyrosol (HT), a strong antioxidant compound from extra virgin olive oil, against TCDD induced toxicity was investigated in human peripheral blood mononuclear cells (PBMC). PBMC (1 × 10⁶ cells mL⁻¹) were divided into four groups and were incubated in a CO₂ incubator (5% CO₂) for 12 h with vehicle, TCDD (10 nM), TCDD + HT (10 nM + 100 μM) and HT alone (100 μM) respectively. To clarify the role of HT against TCDD induced cytotoxicity, oxidative stress and the levels of antioxidant enzymes were assessed. Incubation of PBMC with TCDD significantly decreased cell viability, catalase (CAT) and glutathione peroxidase (GPx) and increased the levels of superoxide dismutase (SOD), glutathione reductase (GR) and oxidative stress markers such as lipid peroxidation products (LPO), protein carbonyl content (PCC) and reactive oxygen species (ROS). Whereas, HT had an effective antioxidant property as observed by the increased cell viability, normalization of antioxidant enzymes and decreased levels of LPO, PCC and ROS in PBMC co-treated with HT and TCDD. Apoptosis detection and comet assay results shows that HT, by acting as an antioxidant, prevents the damage to DNA induced by TCDD. In addition light microscopic and histopathological observations revealed that the cells are apoptotic and degenerated during TCDD treatment, whereas cells showed intact morphology during co-treatment with HT. On the whole, the results reveal that HT exerts a promising antioxidant potential in protecting the PBMC against TCDD induced oxidative stress, which might be due to the presence of catechol moiety in its structure.     

An occupational exposure assessment of polychlorinated dibenzo-p-dioxin and dibenzofurans in firefighters

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are unintentional byproducts of combustion and industrial processes. Firefighters face the risk of occupational exposure to PCDD/Fs. Congener-specific analyses of 17 PCDD/Fs were performed on 20 serum samples collected from firefighters and fire scene investigators, and four soot samples that had deposited on the surfaces of the fire helmets and were collected after the firefighters had fought fires. The PCDD/F concentrations on the helmets that were contaminated by being worn at the fire scenes were 63-285 times higher than those on a clean helmet. The median serum PCDD/F concentration of the 16 firefighters (12 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was not different from those of the males from the general Taiwanese population (9.4 pg WHO₂₀₀₅-TEQ g⁻¹ lipid). However, the median PCDD/F level in the four fire scene investigators (15 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was higher than those in the male from the general Taiwanese population (Mann-Whitney U test, p < 0.01). Furthermore, the serum samples from the firefighters and fire scene investigators, and the soot samples from the fire scenes presented similarly distinctive PCDD/F profiles that had elevated proportions for 10 PCDF congeners. Limited data indicated that the fire scene investigators were occupationally exposed to PCDD/Fs at the fire scenes. We suggested that the firefighters were not occupationally exposed to PCDD/Fs at the fire scenes due to appropriate protection. However, the fire scene investigators may have had more occupational exposure to PCDD/Fs due to poor protection, and further research must be performed to confirm this.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.