Diuron mobility through vineyard soils contaminated with copper

The herbicide diuron is frequently applied to vineyard soils in Burgundy, along with repeated treatments with Bordeaux mixture (a blend of copper sulfate and calcium hydroxide) that result in elevated copper concentrations. Cu could in principle affect the fate and transport of diuron or its metabolites in the soil either directly by complexation or indirectly by altering the populations or activity of microbes involved in their degradation. To assess the effect of high Cu concentrations on diuron transport, an experiment was designed with ten undisturbed columns of calcareous and acidic soils contaminated with 17--509 mg kg(-1) total Cu (field-applied). Grass was planted on three columns. Diuron was applied to the soils in early May and in-ground lysimeters were exposed to outdoor conditions until November. Less than 1.2% of the diuron applied was found in the leachates as diuron or its metabolites. Higher concentrations were found in the effluents from the grass-covered columns (0.1--0.45%) than from the bare-soil columns (0.02--0.14%), and they were correlated with increases in dissolved organic carbon. The highest amounts of herbicide were measured in acidic-soil column leachates (0.98--1.14%) due to the low clay and organic matter contents of these soils. Cu also leached more readily through the acidic soils (32.8--1042 microg) than in the calcareous soils (9.5--63.4 microg). Unlike in the leachates, the amount of diuron remaining in the soils at the end of the experiment was weakly related to the Cu concentrations in the soils.     

Evaluation of copper availability to plants in copper-contaminated vineyard soils

The repeated use of copper (Cu) fungicides to control vine downy mildew has led to long-term accumulation of Cu in vineyard soils which now raises the issue of the potential bioavailability of Cu for various living organisms including plant species. The bioavailable Cu can be defined as the portion of soil Cu that can be taken up by roots, for a given plant species. In order to evaluate the bioavailability of Cu to plants, a pot experiment was conducted in glasshouse conditions with a crop species (maize) and 12 soils sampled in the upper horizon of 10 vineyard plots (total Cu ranging from 38 to 251 mg kg-1) and two woodland plots (control soils that had not received any Cu application; total Cu amounting to 20-26 mg kg-1). These soils were selected for their diverse physical (large range of particle size distribution) and chemical (from acid to calcareous soils) properties. After 35 days of growth, plant shoots were harvested for analysis. The roots were separated from soil particles for further analysis. The concentrations of Cu in the roots and aerial parts of the maize were then compared with the amounts of Cu extracted from the soil by a range of conventional extractants. Observed Cu concentrations in maize roots which have grown in contaminated vineyard soils were very high (between 90 and 600 mg kg-1), whereas Cu concentrations in the aerial parts varied only slightly and remained low (< 18 mg kg-1). Root Cu concentrations observed for maize increased with increasing total Cu content in the soil and with decreasing soil CEC. Cu accumulation in maize roots may be as high in calcareous soils as in acid soils, suggesting that soil pH had little influence. In the case of the vineyard soils studied, the lack of correlation found for maize between Cu concentrations in roots and in the aerial parts, suggests that an analysis of the aerial parts would not be a good indicator of plant Cu uptake, as it provides no insight into the real amount of Cu transferred from the soil to the plant. For maize, our results show that extraction with organic complexing agents (EDTA, DTPA) and extraction with ammonium acetate seem to provide a reasonably good estimate of root Cu concentration.     

Influence of organic amendments on copper distribution among particle-size and density fractions in Champagne vineyard soils

The intensive use for over 100 years of copper sulfate (Bordeaux mixture) to fight against mildew in vineyard soils has led to an important, widespread accumulation of Cu (100 to 1500 mg Cu kg-1 soil). In Champagne vineyards, organic amendments are used currently to increase soil fertility and to limit soil erosion. Organic amendments may have a direct effect on the retention of Cu in the soil. To assess the influence of the organic management on the fate of Cu in calcareous Champagne vineyard soils, we studied Cu distribution (1) in the soil profile and (2) among primary soil particles, in vineyard parcels with different amendments. Amendments were oak-bark, vine-shoots and urban compost. The results were compared with the amount and the distribution of Cu in an unamended calcareous soil. Physical soil fractionations were carried out to separate soil primary particles according to their size and density. Cu has a heterogeneous distribution among soil particle fractions. Two fractions were mainly responsible for Cu retention in soils: the organic debris larger than 50 microns or coarse particulate organic matter (POM) issued from the organic amendments, and the clay-sized fraction < 2 microns. The POM contained up to 2000 mg Cu kg-1 fraction and the clay fraction contained up to 500 mg Cu kg-1 fraction. The clay-sized fraction was responsible for almost 40% of the total amount of Cu in the four parcels. POM was predominantly responsible for the differences in Cu contents between the unamended and the three amended parcels. Our results attested that methods of soil particle-size fractionation can be successfully used to assess the distribution of metal elements in soils.     

Effects of copper concentration on methane emission from rice soils

Outdoor pot experiments with various paddy soils representing five soil types were conducted at Nanjing Agricultural University during the 2000 and 2001 rice-growing seasons. Eighteen soils and ten out of the eighteen soils were involved in the 2000 and the 2001 experiment, respectively. Two treatments were designed as mineral fertilization (MF) and mineral fertilizer + wheat straw incorporation (MF + WS) for the 2001 experiment. Seasonal average rate of CH4 emission from different soils ranged from 1.96 to 11.06 mg m(-2) h(-1) in the 2000 experiment, and from 0.89 to 5.92 mg m(-2) h(-1) for the MF treatment in the 2001 experiment, respectively. Incorporation of wheat straw enhanced considerably CH4 emission with an average increment of 7.09 mg m(-2) h(-1). CH4 emissions from the two-year experiment were negatively correlated to soil available and total copper concentration. A further investigation showed that CH4 emission from the MF treatment was positively related to the dissolved organic carbon (DOC) in the soil (r = 0.904, p < 0.001), and that the DOC was negatively correlated to the concentrations of available copper (r = -0.844, p < 0.01) and total copper (r = -0.833, p < 0.01), respectively. Nevertheless, the incorporation of wheat straw did not enhance the soil DOC, and the relationship between CH4 emission and soil DOC was not statistically significant (r = 0.470, p < 0.20). It was concluded that higher concentration of copper in the soils resulted in lower soil DOC and thus reduced CH4 emission when there was no additional organic matter input. Incorporation of wheat straw did not affect soil DOC and available copper concentration but enhanced CH4 emission.     

Influence of soluble copper on the electrokinetic properties and transport of copper oxychloride-based fungicide particles

This article describes the influence of dissolved copper on the electrokinetic properties and transport of a copper oxychloride-based fungicide (COF) in porous media. The Zeta potential (ζ) of COF particles increases (viz. becomes less negative) with increasing concentration of Cu(2+) in the bulk solution. ζ decreases for COF when the electrolyte (NaNO(3)) concentration is raised from 1 to 10mM. This can be ascribed to ion correlation of Cu(2+) in the electrical double layer (EDL). COF transport tests in quartz sand columns showed the addition of Cu(2+) to the bulk solution to result in increased retention of the metal. Modelling particle deposition dynamics provided results consistent with kinetic attachment. Based on the effect of soluble Cu on colloid mobility, the transport of particulate and soluble forms of copper is coupled via the chemistry of pore water and colloid interactions. Mutual effects between cations and colloids should thus be considered when determining the environmental fate of particulate and soluble forms of copper in soil and groundwater (especially at copper-contaminated sites).     

Effectiveness of control strategies against Botrytis cinerea in vineyard and evaluation of the residual fungicide concentrations

This investigation was undertaken to test different control strategies against Botrytis cinerea vineyards. Two commercial vineyards, “Barbera” and “Moscato,” located in Piedmont (Northern Italy) were divided into seven plots and treated with different combinations of fungicides including fenhexamid, pyrimethanil, fludioxonil + cyprodinil, iprodione, and boscalid, a new carboxamide compound. An integrated strategy including a chemical (pyrimethanil) and a biocontrol agent (Trichoderma spp. t2/4ph1) was also included. At harvest, the percentage of bunches and berries attacked by B. cinerea and the concentration of the chemical fungicides were determined. All the pesticide residues at harvest were below the maximum residue level (MRL), except when two applications of pyrimethanil per season were applied. Boscalid was the most effective active ingredient against B. cinerea among the tested chemicals. When boscalid application was followed by a treatment with pyrimethanil, its efficacy was similar to that shown by two treatments of pyrimethanil. However, this second strategy was not feasible due to the risks of resistance development in the pathogen and to the residue accumulation as indicated by the analysis.     

Effects of metsulfuron‐methyl on microbial biomass and populations in soils

Abstract

Effects of the herbicide metsulfuron‐methyl on soil microorganisms and their activities in two soils were evaluated under laboratory conditions. Measurements included their populations, soil respiration, and microbial biomass. In the clay soil, bacterial populations decreased with increasing concentration of metsulfuron‐methyl during the first 9 days of incubation but exceeded that of the control soil from day 27 onward. In the sandy loam soil, the herbicide reduced bacterial populations during the first 3 days after application, but these increased to the level of untreated controls after 9 days’ incubation. Fungal populations in both soils increased with increasing metsulfuron‐methyl concentrations, especially in the sandy loam soil. CO₂ evolution was stimulated in both soils in the presence of the herbicide initially, but decreased during days 3 to 9 of the incubation period before increasing again afterward. The presence of metsulfuron‐methyl in the soil increased microbial biomass, except in sandy loam soil at the first day of incubation.     

Persistence of hexaconazole, a triazole fungicide in soils

Persistence of hexaconazole (2-(2,4-dichlorophenyl)- 1-(1H-1,2,5-triazol-1-yl) hexan-2-ol) was studied in alluvial, red and black soils under flooded and nonflooded conditions. This fungicide was more persistent in all soils under flooded conditions than under nonflooded conditions and at 27 degrees C than at 35 degrees C. Degradation of hexaconazole in sterilized and nonsterilized soils proceeded at identical rates indicating a minor role of micro-organisms in its degradation. The soil persistence of hexaconazole was not affected by the addition of wheat straw both under flooded and nonflooded conditions.     

Persistence of hexaconazole,a triazole fungicide in soils

Abstract

Persistence of hexaconazole (2‐(2,4‐dichlorophenyl)‐l‐(lH‐l,2,5‐triazol‐l‐yl) hexan‐2‐ol) was studied in alluvial, red and black soils under flooded and nonflooded conditions. This fungicide was more persistent in all soils under flooded conditions than under nonflooded conditions and at 27°C than at 35°C. Degradation of hexaconazole in sterilized and nonsterilized soils proceeded at identical rates indicating a minor role of micro‐organisms in its degradation. The soil persistence of hexaconazole was not affected by the addition of wheat straw both under flooded and nonflooded conditions.     

Effects of environmental factors on organochlorine pesticide residues in soils of the Guanting Reservoir area, China

Topsoil samples from 56 sites around the Guanting Reservoir, China, were measured for HCH and DDT concentrations. The total soil HCH content (including alpha-, beta-, gamma-, and delta-isomers) in these soil samples ranged from 0 to 7.33 ng x g(-1), with a mean of 0.69 ng x g(-1). These levels were considerably lower than those of the total DDT soil contents (including pp'-DDE, pp'-DDD, op'-DDT, and pp'-DDT), which ranged from 0 to 76.01 ng x g(-1), with a mean of 9.46 ng x g(-1). DDT was also found to be the major pollutant in the soil samples, accounting for approximately 93% of the total organochlorine pesticide (OCP) contents. Several environmental factors including land use, soil texture, soil taxonomy, and microbial biomass were considered to be responsible for the OCP levels observed. The data provide some insight into the effects of environmental conditions such as soil formation, agricultural cultivation, nutrient enrichment, and other anthropogenic activities on the degradation of OCPs in soils. Although the OCP residues currently are below the maximum limits set for use on agricultural land in China, and only rarely would such levels pose significant ecological concern, OCPs are highly persistent in soil and bioaccumulative. The data provided in this study are considered crucial for reservoir remediation, especially since the Guanting Reservoir will serve as one of the main drinking water sources for Beijing in the foreseeable future.     

Effects of sensitizers on the photodegradation of the systemic fungicide triadimenol

The photochemical behaviour of triadimenol (1) under various conditions has been examined. Significant degradation is obtained only in the presence of electron-acceptor sensitizers as 9,10-dicyanoanthracene or 2,4,6-triphenylpyrylium tetrafluoroborate, and long irradiation times are required. 1H-1,2,4-Triazole (2), 4-chlorophenyl formate (3), 4-chlorophenol (4), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (5), 4-chlorophenyl 2,2-dimethylpropanoate (6) and 4-chlorobenzoic acid (7) were identified as photoproducts by NMR and GC-MS.     

Metal contamination of vineyard soils in wet subtropics (southern Brazil)

The vine-growing areas in Brazil are the dampest in the world. Copper maximum value registered in this study was as much as 3200 mg kg(-1), which is several times higher than reported for vineyard soils in temperate climates. Other pesticide-derived metals accumulate in the topsoil layer, surpassing in the old vineyards the background value several times for Zn, Pb, Cr and Cd. Copper is transported to deeper soils' horizons and can potentially contaminate groundwater. The soils from basaltic volcanic rocks reveal the highest values of Cu extracted with CaCl(2), demonstrating a high capacity of copper transference into plants. When evaluating the risks of copper's toxic effects in subtropics, the soils from rhyolitic volcanic rocks are more worrisome, as the Cu extracted with ammonium acetate 1M surpasses the toxic threshold as much as 4-6 times.     

Effect of copper on the adsorption of p-nitrophenol onto soils

The effect of copper on adsorption of p-nitrophenol on two typical Chinese soils was investigated using a batch-equilibration method. Adsorption experiments were carried out when both copper and p-nitrophenol were adsorbed simultaneously, and when copper was previously adsorbed on soils. It was observed that adsorption of p-nitrophenol decreased with increasing copper concentrations thereby indicating a competition between copper and p-nitrophenol for occupying the adsorption sites on soils. Moisture increased the hydrated sphere and the acidity of water surrounding the cation, which further reduced the adsorption of p-nitrophenol. Fourier transform infrared spectroscopy study provided the direct evidence for the coordination of p-nitrophenol sorbed by soils with metal cation in n-hexane system. It was observed that the perturbations included a red shift of the nu(asym) (NO) band, a concomitant blue-shift of the nu(sym) (NO) band and a blue-shift of C-N band when compared with the infrared spectra obtained from water solution.     

Effect of glyphosate on the microbial activity of two Brazilian soils

Glyphosate [N-(phosphonomethyl)-glycine] is a broad-spectrum, non-selective, post-emergence herbicide that is widely used in agricultural. We studied, in vitro, changes in the microbial activity of typical Hapludult and Hapludox Brazilian soils, with and without applied glyphosate. Glyphosate was applied at a rate of 2.16 mg glyphosate kg(-1) of soil and microbial activity was measured by soil respiration (evolution of CO(2)) and fluorescein diacetate (FDA) hydrolysis over a period of 32 days. We found an increase of 10-15% in the CO(2) evolved and a 9-19% increase in FDA hydrolyses in the presence of glyphosate compared with the same type of soil which had never received glyphosate. Soil which had been exposed to glyphosate for several years had the strongest response in microbial activity. Most probable number (MPN) counts showed that after 32 days incubation the number of actinomycetes and fungi had increased while the number of bacteria showed a slight reduction. After the incubation period, high pressure liquid chromatography (HPLC) detected the glyphosate metabolite aminomethyl phosphonic acid (AMPA), indicating glyphosate degradation by soil microorganisms.     

作物种类对中国2种典型土壤中铜锌有效性的影响

为阐明不同作物对土壤铜锌有效性的影响,采集2种典型土壤--红壤和黄泥土,人工制成铜锌单一与复合污染的土壤(铜为50 mg/kg、锌为200 mg/kg),进行盆栽试验,观察了小麦、油菜、番茄和小白菜4种作物的生物量、铜锌浓度及土壤有效态铜锌浓度.结果表明:(1)在2种土壤上,4种作物的生物量均小于没有污染的对照,且铜锌复合污染的作物生物量总体上比铜锌单一污染的低;(2)4种作物在红壤和黄泥土上种植对土壤有效态铜、锌浓度影响的趋势一致,均为种植番茄后铜锌污染土壤的有效态铜、锌浓度最高,油菜和小白菜次之,小麦最低,即番茄>油菜和小白菜>小麦,与作物中铜、锌浓度以及富集系数的高低顺序完全相反;(3)对照、铜锌单一与复合污染土壤pH变化均不甚明显;(4)作物对土壤铜锌有效性的影响并不只是通过提高土壤pH来降低有效态铜、锌浓度,对铜锌的吸收富集作用是降低其有效性的主要机制之一.     

Speciation and origin of particulate copper in runoff water from a Mediterranean vineyard catchment

Fungicide treatments have led to large copper contents of the topsoils of most vineyards. This paper examines the contamination of surface waters by copper in a Mediterranean wine-growing catchment. Its aims were to characterise the forms of copper associated with suspended matter during a heavy autumn storm event and to identify which soils contribute the most to the copper exports. A mixing model involving three reservoirs, corresponding to three soil-landscape units (plateau, terraces and footslope-depression system) and two tracers (reducible iron content and dolomite/calcite ratio) was used to estimate the contribution of each reservoir to erosion during a storm flow. The average copper concentration of the suspended matter was 245 mg kg(-1), of which 1% was exchangeable, 4% acid-soluble, 10% oxidizable, 23% reducible and 63% residual. The soils of the plateau of the catchment (chromic luvisols and haplic calcisols-FAO soil classification) were the source of 42% of copper exports but represented only 27% of the total catchment area.     

铜对活性污泥微生物活性影响研究

通过人工投加铜离子对驯化污泥的破坏性实验,研究了各浓度铜离子对活性污泥氨氮、COD降解的影响及其TTC-脱氢酶活性、氧摄取速率(SOUR)、氨摄取速率(AUR)的影响。结果显示,0~5 mg/L的铜离子对处理系统有机物的去除率影响不大。铜离子浓度与活性污泥的TTC-脱氢酶活性、SOUR以及AUR之间呈现良好的相关性;低浓度的铜离子对TTC-脱氢酶活性和SOUR均有一定的促进作用,而对AUR则会产生一定的抑制作用。当铜离子浓度达到5 mg/L时,其对SOUR、TTC-脱氢酶活性以及AUR的抑制率均超过50%。在此情况下,采用TTC-脱氢酶活性、SOUR以及AUR等指标,能快速有效地表征铜离子对活性污泥微生物的毒害作用。     

Effects of alkaline dust deposits from phosphate fertilizer production on microbial biomass and enzyme activities in grassland soils

Microbial biomass carbon (Cmic) and soil enzyme activities were measured at 12 sites along a gradient of former emissions of phosphate fertilizer production. Seven years after close down of operation, still moderate to high total concentrations of the dust constituents cadmium (up to 33 mg kg-1 dw), fluoride (5300 mg kg-1 dw) and phosphorous (120,000 mg kg-1 dw) were found in topsoils of contaminated sites. Accumulation of partially decomposed plant matter, soil respiration and dehydrogenase activity paralleled the increase of dust deposits, whereas microbial biomass decreased along the gradient. A significant negative correlation was obtained between the Cmic-to-Corg-ratio and the concentration of contaminants. In contrast, the Cmic-specific respiration (qCO2) and the dehydrogenase activity-to-Cmic-ratio were positively correlated. The low Cmic-values and the enhanced activities in the contaminated soils are suggested as a response of microbial communities to environmental stress or ecosystem disturbances. The apparently missing detrimental effects of the alkaline deposits on soil microbial activities are probably due to the low bioavailability of contaminants in the calcareous soil.     

Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.