Response of the bacteria and fungi of two soils to the sulfonylurea herbicide cinosulfuron.

Changes in aerobic bacteria and autotrophic nitrifier numbers, and in respiration and nitrification in two soils treated with cinosulfuron at 42 (field rate) and 4200 microg/kg were studied after 1 and 4 weeks of incubation under laboratory conditions. Only nitrification at 1 week was slightly inhibited by the cinosulfuron treatment, even at the field rate. In vitro toxicity tests carried out in agar media on representative aerobic bacteria, fungi and Azotobacter strains isolated from the two soils, as well as on nine collection soil bacteria, showed that only a very high cinosulfuron concentration (100 mg/l) can have negative effects on the growth of a limited number of soil heterotrophic microorganisms, under conditions similar to those of soil environment. The absence of three branched-chain amino acids increased bacterial sensitivity, thus showing the importance of the chemical conditions and suggesting acetolactate synthase enzyme blockage as the toxicity mechanism. It is concluded that cinosulfuron has a negative effect on only a few aspects of the microbial community in soil ecosystems, even at concentrations higher that those currently in use.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Aquatic risk assessment of the new rice herbicide profoxydim

A tiered protocol for assessing ecological risks has been applied to the rice pesticide profoxydim. The initial assessment (Tier I) was based on toxicity exposure ratio (TER) calculations based on laboratory data using a worst-case rice scenario. The first refinement (Tier II) was based on direct toxicity assessment (DTA) of water samples collected during a field-mesocosm study. Finally, a higher-tier assessment on the in situ assessment of paddy community responses (field-mesocosm-Tier III) was performed. A successive application of three pesticides, the herbicides azimsulfuron, propanil and the insecticide malathion, was used as reference controls. The refined assessments indicated a lower risk than that predicted from TER estimations. DTA-based Tier II showed toxicity effects only for concentrations above the recommended dose of profoxydim. Effects for reference controls were observed in DTA which were not expected from Tier I. The field-mesocosm study confirmed these effects but also showed that they were transient and of low relevance.     

Variations of arsenic species content in edible Boletus badius growing at polluted sites over four years

The content of arsenic (As) in mushrooms can vary depending on the concentration level of this metalloid in the soil/substrate. The present study evaluated the content of arsenic in Boletus badius fruiting bodies collected from polluted and non-polluted sites in relation to the content of this element in overgrown substrate. It was found that mushrooms from the arsenic-polluted sites contained mean concentrations from 49 to 450 mg As kg^?1 dry matter (d.m.), with the greatest content found for specimens growing in close proximity of sludge deposits (490±20 mg As kg^?1d.m.). The mean content of total arsenic in mushrooms from clean sites ranged from 0.03 to 0.37 mg kg^?1 It was found that B. badius could tolerate arsenic in soil substrate at concentrations of up to 2500 mg kg^?1, at least. In different years of investigation, shifts in particular arsenic forms, as well as a general increase in the accumulation of organic arsenic content, were observed. The results of this study clearly indicate that B. badius should not be collected for culinary purposes from any sites that may be affected by pollution.     

4种湿地植物对人工湿地净化生活污水的影响比较

不同类型人工湿地对生活污水的处理效果,受到许多因素的影响,其中不同植物类型的选择,可能会造成人工湿地对主要污染物COD、TN和TP的净化效果发生很大差异。研究了4种湿地植物（菖蒲、香蒲、千屈菜和水葱）在水平潜流、垂直上行流和下行流人工湿地中对人工合成的生活污水的处理效果和主要污染物（COD、TN和TP）去除率的季节变化,通过比较不同植物类型在不同湿地类型中对主要污染物的去除效果分析了可以达到最佳污水净化效果的启动条件。结果表明：香蒲在垂直下行流湿地去除有机污染物效果最好,去除率可达85.55%;水葱在垂直上行流湿地去除TN效果最好,去除率可达57.52%,香蒲在垂直上行流湿地去除TP效果最好,去除率可达84.28%。     

Long-term projection of future climate change over the twenty-first century in the Sahara region in Africa under four Shared Socio-Economic Pathways scenarios

Environmental Science and Pollution Research - Climate change affects air quality and people’s health. Therefore, accurate prediction of future climate change is of great significance for...     

Environmental fate and non-target impact of glyphosate-based herbicide (Roundup) in a subtropical wetland

Mai Po Nature Reserve (Hong Kong) is an internationally important wetland for waterbirds. Roundup, a formulation based on glyphosate, has been used to control the widespread weeds within the reserve for many years but the fate and non-target impact of the herbicide is unknown. To fill this knowledge gap, we applied Roundup by hand-held sprayer to an estuarine and a freshwater pond in the dry season of year 2002. The surface water and sediment were sampled routinely for glyphosate concentrations following one month of application. In situ bioassays using local edible fish species were performed along with the herbicide application. Up to 52% of glyphosate in the surface water was transported to the unapplied regions by wind-driven current in the estuarine pond at 1 DPT (day post treatment). For both ponds, glyphosate concentrations in the water decreased rapidly after 1-3 DPT, but then decreased gradually over time. Both physical adsorption to the bottom sediments and microbial degradation are thought to contribute to these decreases. Interestingly, the persistence of glyphosate in the freshwater pond was longer than in the estuarine system, which is likely due to the considerably higher concentrations of chelating metals (i.e. Cu and Fe) present in the sediment (4.5 and 11-fold higher, respectively) which potentially reduced the bioavailability of glyphosate to the microbial decomposers. Lastly, fishes used in the in situ bioassays (both in applied and unapplied areas) showed similar survival rates, indicating that the use of Roundup at the provided application rate posed no serious hazard.     

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.     

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.     

Long-term trends in Swiss rivers sampled continuously over 39 years reflect changes in geochemical processes and pollution

Environmental Science and Pollution Research - Long-term changes of 14 water constituents measured in continuously and water discharge proportionally collected samples of four Swiss rivers over a...     

Growth rate effects, responses of antioxidant enzymes and metabolic fate of the herbicide Propanil in the aquatic plant Lemna minor

Propanil (3,4-dichloropropionanilide) is a selective contact pesticide, recommended for post-emergence use in rice. This herbicide may end up in surface waters and present potential risk for aquatic vascular plants. Therefore, its toxicity was evaluated on Lemna minor L., an aquatic plant regularly used for toxicological studies, during time- and concentration-dependent exposure. Toxicity assessments were based on inhibition of growth of L. minor cultures after 24 days. The obtained results showed that the growth of Lemna was affected by the herbicide. The responses of the guaiacol peroxidase (G-POD) and glutathione S-transferase (GST) involved in the xenobiotic metabolism and antioxidative system were also investigated following Propanil exposure. Our results showed that Propanil has not induced enzymatic antioxidative defenses of L. minor. Both 3,4-dichloroaniline (3,4-DCA) and 3,4-dichloroacetanilide are the major metabolites in this plant. On the contrary, only 3,4-DCA was found in culture media after 4 days. Probably, the enzymatic hydrolysis by acyl acylamidase and the acetylation by acetyl-CoA are the major pathways for these transformation products, respectively. The results of this study showed that the selected aquatic plant has the potential to accumulate and metabolize rice herbicide, like Propanil. Based on these toxicity data this herbicide should impair the establishment of non-target aquatic plants.     

Occurrence and fate of four novel brominated flame retardants in wastewater treatment plants

Four novel brominated flame retardants (NBFRs), i.e., decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB) were studied in 377 liquid samples and 288 solid samples collected from 20 wastewater treatment plants. Lagoon, primary, secondary, and advanced treatment processes were included, in order to investigate NBFR occurrence and the effects of WWTP operational conditions on NBFR removal. Median influent and effluent levels were 14 to 3,700 and 1.0 to 180 pg/L respectively, with DBDPE being the highest in both. Overall median removal efficiencies for DBDPE, BTBPE, HBB, and PBEB across all process types were 81 to 93, 76 to 98, 61 to 97, and 54 to 97 %, respectively with advanced treatment processes obtaining the best removals. NBFRs removal was related to retention time, surface loading rate, and biomass concentration. Median NBFR levels in treated biosolids were 80 to 32,000 pg/g, influenced by solids treatment processes.     

Progress in herbicide determination with the thylakoid bioassay

Chloroplast thylakoids are used as biological units to determine herbicides in different kinds of water samples as well as in aqueous extracts of compost, soil or food samples. The thylakoid bioassy shows clearly inhibition of fluorescence yield in the presence of photosystem II specific herbicides. Due to this method the ecotoxicological effect of samples with unknown pollutants can be tested fast and cost effective. It has been proven that all photosynthetic active compounds are recorded at the same time because only additive interactions occur. Therefore, the contamination level can be expressed as cumulative parameter for photosystem II active substances. Application was improved clearly by the addition of the radical scavenger sodium ascorbate to the isolation media and by a higher concentration of the measuring medium. A new data evaluation method is described yielding in a lower detection limit of 0.4 μg diuron/1. The guidelines for the quality of water for human consumption with an allowable concentration of pesticides in groups is 0,5 μg/1 [1,2] and can be controlled with the thylakoid bioassay without performing any preconcentration steps.     

Evaluation of pressurized liquid extraction for the analysis of four pesticides in unpolished rice

The aim of to evaluate efficiency of this study was extraction pressurized liquid extraction (PLE) for the analysis of four pesticides, fthalide, etofenprox, fenitrothion, and isoprothiolane, in unpolished rice by comparing with homogenization as a reference technique. The concentrations of four selected pesticides obtained by PLE with acetonitrile at 130°C for 10 min × 2 cycles were comparable to those by homogenization with water-soaking. The repeatability of the analysis, represented as relative standard deviations (RSDs), were 1.4–3.6% (n = 3) for PLE at 130°C and 1.2–3.8% (n = 3) for homogenization with water-soaking. Recovery yields of surrogates were 75–88% and 87–109% for PLE at 130°C and homogenization with water-soaking, respectively, and these were satisfactory according to the method of positive list. This study suggested that PLE can be applied for the analysis of selected four pesticides in unpolished rice as well as homogenization with water-soaking.     

Evaluation of pressurized liquid extraction for the analysis of four pesticides in unpolished rice

The aim of to evaluate efficiency of this study was extraction pressurized liquid extraction (PLE) for the analysis of four pesticides, fthalide, etofenprox, fenitrothion, and isoprothiolane, in unpolished rice by comparing with homogenization as a reference technique. The concentrations of four selected pesticides obtained by PLE with acetonitrile at 130 degrees C for 10 min x 2 cycles were comparable to those by homogenization with water-soaking. The repeatability of the analysis, represented as relative standard deviations (RSDs), were 1.4-3.6% (n = 3) for PLE at 130 degrees C and 1.2-3.8% (n = 3) for homogenization with water-soaking. Recovery yields of surrogates were 75-88% and 87-109% for PLE at 130 degrees C and homogenization with water-soaking, respectively, and these were satisfactory according to the method of positive list. This study suggested that PLE can be applied for the analysis of selected four pesticides in unpolished rice as well as homogenization with water-soaking.     

Fate of caffeine in mesocosms wetland planted with Scirpus validus

Uptake, accumulation and translocation of caffeine by Scirpus validus grown in hydroponic condition were investigated. The plants were cultivated in Hoagland’s nutrient solution spiked with caffeine at concentrations of 0.5–2.0 mg L^?1. The effect of photodegradation on caffeine elimination was determined in dark controls and proved to be negligible. Removal of caffeine in mesocosms without plants showed however that biodegradation could account for about 15–19% of the caffeine lost from solutions after 3 and 7 d. Plant uptake played a significant role in caffeine elimination. Caffeine was detected in both roots and shoots of S. validus. Root concentrations of caffeine were 0.1–6.1 μg g^?1, while the concentrations for shoots were 6.4–13.7 μg g^?1. A significant (p < 0.05) positive correlation between the concentration in the root and the initial concentrations in the nutrient solution was observed. The bioaccumulation factors (BAFs) of caffeine for roots ranged from 0.2 to 3.1, while BAFs for shoots ranged from 3.2 to 16.9. Translocation from roots to shoots was the major pathway of shoot accumulation. The fraction of caffeine in the roots as a percentage of the total caffeine mass in solution was limited to 0.2–4.4% throughout the whole experiment, while shoot uptake percentage ranged from 12% to 25% for caffeine at the initial concentration of 2.0 mg L^?1 to 50–62% for caffeine at the initial concentration of 0.5 mg L^?1. However, a marked decrease in the concentration of caffeine in the shoots between d-14 and d-21 suggests that caffeine may have been catabolized in the plant tissues subsequent to plant uptake and translocation.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Long-term changes in the tropospheric column ozone from the ozone soundings over Europe

The tropospheric column of ozone is analyzed from the measurements of the vertical profile of ozone by balloon-born ozonesondes. The data base includes ∼16,000 ozone profiles collected above six European stations—three of them have begun the ozonesoundings since 1970. We present a trend analysis (with data up to 2005) focusing on detection of the long-term tropospheric ozone variability over the European network. The ozone time series have been examined separately for each station and season (DJF, MAM, JJA, SON) using a flexible trend model. A trend component of the model is taken as a smooth curve without a priori defined shape. A large increase in the European tropospheric ozone since the beginning of the 1970s (net change of ∼10% in summers and ∼30% in winters) and a kind of stabilization in the early 1990s have been corroborated by the study. This pattern comes from the most extensive data set of ozonesoundings over Hohenpeissenberg and Payern. The decadal differences in the trend pattern between these and other European stations are disclosed. The results of a stepwise regression model using various characteristics of the ozone and temperature profiles as explanatory variables for the tropospheric column ozone (TCO₃) variations show that the ozone changes may be reconstructed using the ozone mixing ratio at 500 hPa, the thermal tropopause (TT) height, and the difference between ozonepause and TT heights. It appears that the last two factors induce 20–30% of the net TCO₃ change over Hohenpeissenberg in the 1970–2004 period.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption-desorption processes. Four soils from Melozal (35° 43' S; 71° 41' W), Parral (36° 08' S; 71° 52' W), San Carlos (36° 24' S; 71° 57' W), and Panimavida (35° 44' S; 71° 24' W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g?1) and were related to soil pH. Molinate showed K(d) values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g?1 and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K(d) values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g?1. MCPA K(d) ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Long-term effects of fertilization on the forms and availability of soil phosphorus in rice paddy

The changes in total P accumulation and P compounds with time in the plough layer in a paddy soil in southern Korea were investigated in relation to the continuous application of chemical fertilizers (NPK), straw based compost (Compost), combination these two (NPK+Compost) for 31 years. Continuous fertilization increased the total and inorganic P contents in plough layers. In NPK, inorganic P fraction did not change with time, but organic P content increased significantly. Long-term application of chemical fertilizer together with compost accelerated the decrease in the organic P fraction, presumably due to promoting microbial activity in the plow layer, and then increased significantly inorganic P fraction. Compost application decreased the residual P and Fe-P fractions and then increased inorganic P fraction, in spite of continuous compost application. Increase in total, inorganic and extractable P with time may be closely related to the increase in the availability of accumulated P for rice growth.