Impact of a smelter closedown on metal contents of wheat cultivated in the neighbourhood

BACKGROUND: The contamination of soils by heavy metals engenders important environmental and sanitary problems in Northern France where a smelter has been located for more than one hundred of years. It has been one of the most important Pb production sites in Europe until its closedown in March 2003. Ore smelting process generated considerable atmospheric emissions of dust. Despite an active environmental strategy, these emissions were still significant in 2002 with up to 17 tonnes of Pb, 32 tonnes of Zn and 1 tonne of Cd. Over the years, the generated deposits have led to an important contamination of the surrounding soils. Previous studies have shown pollutant transfers to plants, which can induce a risk for human and animal health. The objective of this study was to evaluate the consequences of the smelter closedown on the Cd and Pb contents of wheat (grain and straw) cultivated in the area. METHODS: Paired topsoil and vegetable samples were taken at harvest time at various distances to the smelter. The sample sites were chosen in order to represent a large range of soil metal contamination. Sampling was realised on several wheat harvests between 1997 and 2003. 25 samples were collected before the smelter closedown and 15 after. All ears of about 1 m long of two rows were manually picked and threshed in the lab. Similarly, straw was harvested at the same time. Total metal contents in soil and wheat samples were quantified. RESULTS: A negative correlation between metal concentrations in soil and the distance to the smelter was shown. The wheat grain and straw showed significant Cd and Pb contents. The straw had higher metal contents than the grain. During the smelter activity, the grain contents were up to 0.8 mg kg(-1) DM of Cd and 8 mg kg(-1) DM of Pb. For the straw, maximum contents were 5 mg kg(-1) DM of Cd and 114 mg kg(-1) DM of Pb. After the smelter closedown, we observed a very large decrease of Pb in the grain (82%) and in the straw (91%). A smaller decrease was observed for Cd in grain. Despite this improvement, 80% of the studied samples remained non-acceptable for human consumption, according to the European legislation values, due to a high Cd content. DISCUSSION: Results highlighted a difference in metal accumulation in the plant organs as well as a difference in metal uptake. The approach pointed out the importance of atmospheric fallout in the wheat contamination pathways for Pb. The smelter closedown has lead to a decrease of the Pb content in wheat. It is interesting to relate this finding with the lead blood levels in children living close to the smelter. CONCLUSIONS: Those results have confirmed the importance of dust fallout in the plant contamination pathways. Before the closedown, Pb measured in the plant was principally originating from the smelter dust emissions. It raised the question of the sanitary risks for humans and animals living in the surrounding a of the smelter. RECOMMENDATIONS AND PERSPECTIVES: In the literature, very few articles take the dust deposit as contamination pathways for crops into consideration. However, in highly contaminated sites, this pathway can be very important. Thus, it would be worthy studying the uptake of metal contaminants by plants through the foliar system.     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 micro g g(-1). The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4-6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

Persistence of herbicide fenoxaprop ethyl and its acid metabolite in soil and wheat crop under Indian tropical conditions

The persistence of fenoxaprop ethyl {Ethyl (RS)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionate} herbicide and its active metabolite fenoxaprop acid was investigated in soil and wheat crop. Fenoxaprop acid was prepared by alkaline hydrolysis of fenoxaprop ethyl. A HPLC method was developed in which fenoxaprop ethyl herbicide and its acid metabolite showed sharp single peak at 6.44 and 2.61 min respectively. The sensitivity of the method for ester and acid was 2 and 1 ng respectively with limit of detection of 0.1 and 0.05 μg mL^?1. The recovery of fenoxaprop ethyl and fenoxaprop acid from soil, wheat straw and grain ranged between 73.8–80.2%. In a field experiment fenoxaprop ethyl (Puma super® 10 EC) when applied to wheat crop at the rate of 120 g and 240 g a.i. ha^-1 as post emergence spray, fenoxaprop ethyl converted to fenoxaprop acid. Residues of fenoxaprop ethyl and acid dissipated in soil with a half-life of 0.5 and 7.3 days, respectively. At harvest no detectable residues of fenoxaprop ethyl or acid were observed in soil, wheat grain and straw samples.     

Dissipation of sulfosulfuron in water - bioaccumulation of residues in fish - LC-MS/MS-ESI identification and quantification of metabolites

Dissipation study of sulfosulfuron in natural water and its bioaccumulation in fish was conducted at 25+/-2 degrees C and at two different concentration levels 1mgl(-1) and 2mgl(-1). The dissipation data in water showed the DT50 and DT90 values 67-76 and 222-253 days and followed first order kinetics. Bioaccumulation of sulfosulfuron in fish was conducted under static conditions exposing the fish at one-tenth of sub-lethal concentration 9mgl(-1) and at double the concentration 18mgl(-1), for a period of 56 days. On different occasions fish samples were collected and analyzed. A HPLC-RF method was used for the quantification of sulfosulfuron and aminopyrimidine with the limit of quantification 0.001microg ml(-1). Results showed the accumulation of residues of sulfosulfuron in fish over the concentration range 0.009-0.496microg g(-1). Both in water and fish samples, identified the presence of metabolites aminopyrimidine, desmethyl sulfosulfuron, guanidine, sulfonamide, ethyl sulfone and rearranged amine. The formations of these metabolites are confirmed by LC-MS/MS analysis. An LC-MS/MS electro spray ionization technique was used for this purpose. One of the metabolite Aminopyrimidine was identified at higher concentration levels (0.01-0.1microg ml(-1)) when compared with other metabolites. Subsequently dissipation of aminopyrimidine in water and its bioaccumulation was also studied at the concentration level 1mgl(-1) and 2mgl(-1). The calculated DT50 and DT90 values are 66-68 days and 218-226 days, respectively. This followed first order kinetics. Three hundred days after the exposure complete demineralization was observed.     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 μ g g^{? 1}. The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4–6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

Determination of acibenzolar-S-methyl and its acidic metabolite in soils by HPLC-diode array detection

A simple and accurate method for the analysis of acibenzolar-S-methyl (benzo[1,2,3]thiadiazole-7-carbothioic acid-S-methyl ester; CGA 245 704; ASM) and its major conversion product, benzo[1,2,3]thiadiazole-7-carboxylic acid (CGA 210 007; BTC), in soils is presented. ASM extraction from soil samples was performed using acetonitrile and BTC was extracted with a mixture of potassium phosphate buffer (0.5 M, pH 3) and acetonitrile (70:30 %, v/v). Both extracts were directly analyzed in a high-performance liquid chromatography-diode array detection (HPLC-DAD) system. Pesticide separation was achieved on a C18 (4.6 mm × 150 mm, 5 μm) analytical column with a isocratic elution of acetonitrile:water 40:60 % (v/v) with 0.6 mL L?1 acetic acid at a flow rate of 1 mL min?1. Linear regression coefficients (r (2)) of the external calibration curves were always above 0.9997. The limits of detection (LOD) and quantification (LOQ) of the method were 0.005 and 0.02 mg kg?1 for ASM, and 0.01 and 0.05 mg kg?1 for BTC, respectively. Recoveries were investigated at six fortification levels and were in the range of 90-120 % for ASM and 74-96 % for BTC with relative standard deviations (RSDs) below 11 % in all cases. The method was also validated by analyzing freshly spiked soil samples with 2.7% organic matter content at 0.5 mg kg?1 level, with slightly lower recovery values only for ASM. Moreover, recoveries for intermediate aged residues of the analytes were similar to fresh residues. This method was also applied to determine ASM half-life (t(?) = 8.7 h) and the rate of the acidic metabolite formation.     

Factors affecting the concentrations of lead in British wheat and barley grain

The entry of Pb into the food chain is of concern as it can cause chronic health problems. The concentration of Pb was determined in cereal grain samples collected representatively from British Cereal Quality Surveys in 1982 and 1998 (n = 176, 250 and 233 for wheat collected in 1982 and 1998, and barley in 1998, respectively). In addition, paired soil and grain samples were collected from 377 sites harvested across Britain in 1998-2000. Wheat grain Pb ranged from below the analytical detection limit (0.02 mg kg(-1) dry weight, DW) to 1.63 mg kg(-1) DW, and barley grain Pb from <0.02 to 0.48 mg kg(-1) DW. The vast majority of samples (>99% for both wheat and barley, excluding Scottish barley samples collected in 2000) were well below the newly introduced EU limit for the maximum permissible concentration of Pb in cereals (0.2 mg kg(-1) fresh weight, equivalent to 0.235 mg kg(-1) DW). There was a significant reduction in wheat grain Pb in the 1998 survey compared with the 1982 survey. However, 40 barley samples collected from Scotland in 2000 in the paired soil and crop survey showed anomalously high concentrations of Pb, with 10 samples exceeding the EU limit. Washing experiments demonstrated that surface contamination, introduced during grain harvest and/or storage, was the main reason for the high concentrations in these samples. In the paired soil and crop surveys, there were no significant correlations between grain Pb concentrations with total soil Pb and other soil properties, indicating low bioavailability of Pb in the soils and limited uptake and transport of Pb to grain. The Pb in cereal grain is likely to originate mainly from atmospheric deposition and other routes of surface contamination during harvest and storage.     

Residues of chlorantraniliprole in rice field ecosystem

The fate of chlorantraniliprole was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of chlorantraniliprole in soil, rice straw, paddy water and brown rice. Chlorantraniliprole residues were extracted from samples with acetonitrile. The extract was cleaned up with QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, and determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The average recoveries were 76.9-82.4% from soil, 83.6-89.3% from rice straw, 95.2-103.1% from paddy water and 84.9-87.7% from brown rice. The relative standard deviation was less than 15%. The limits of detection (LODs) of chlorantraniliprole calculated as a sample concentration (S/N ratio of 3) were 0.012 μg L(-1) for paddy water, 0.15 μg kg(-1) for soil, brown rice and rice straw. The results of the kinetics study of chlorantraniliprole residue showed that chlorantraniliprole degradation in soil, water and rice straw coincided with C=0.01939e(-0.0434t), C=0.01425e(-0.8111t), and C=1.171e(-0.198t), respectively; the half-lives were about 16.0 d, 0.85 d and 3.50 d, respectively. The degradation rate of chlorantraniliprole in water was the fastest, followed by rice straw. The final residues of chlorantraniliprole on brown rice were lower than maximum residue limit (MRL) of 0.02 mg kg(-1) after 14 d Pre-Harvest Interval (PHI). Therefore, a dosage of 150 mL a.i.hm(-2) was recommended, which could be considered as safe to human beings and animals.     

Cadmium availability to wheat in five soil series from the Yonne district, Burgundy, France

Preliminary results from the French ASPITET programme demonstrated that Cd background levels in agricultural soils can vary greatly (0.02-6.9 mg Cd kg(-1)) depending on parent material and pedogenic processes (Baize, 1997). However, the total Cd content in soil is often not significantly related to the Cd concentration in edible plant parts. A field case study was undertaken across the southern part of the Yonne district, Burgundy, France. This area has various soil series with either low or high geochemical Cd content in the topsoil. Cd availability in soils sampled at 16 sites belonging to five soil series was investigated using single extractions. In addition, shoots (at stem elongation) and grains (at harvest) of field-grown wheat were collected at the same sites and analysed for macronutrients and trace elements. Cd concentrations in grain varied from 0.015 to 0.146 mg Cd kg(-1) DM depending on soil characteristics, soil series, and plant mineral composition. Cd grain concentrations did not reflect total Cd content in the surface soil layer; however, they were correlated with Cd extracted by a 0.1 M calcium nitrate unbuffered solution, and to a lesser extent with either soil pH or CEC. These three parameters may be useful guides to predict Cd in wheat grain harvested in the Yonne district. An inverse relationship was found between Cd and Cu contents in grain. The highest Cd concentrations in wheat grain occurred in plants grown on Aubues soils which had marginal Cu and Zn deficiencies in shoots. In order of Cd accumulation in wheat grain, soil series may be ranked as follows: Domérien < Carixien, Terres Noires < Sols Marron < Aubues.     

Dissipation of DDT in a heavily contaminated soil in Mato Grosso, Brazil

After the prohibition of organochlorine-pesticide use in Brazil for controlling insect vector diseases, Mato Grosso State gathered the exceeding DDT and stored it irregularly in an open air area that belongs to the National Health Foundation, causing soil contamination. This study aimed to evaluate the contamination level and dissipation of p,p'-DDT and p,p'-DDE in this area. For that, surface soil samples were collected on 19 September 2000, 15 December 2000, 4 April 2001 and soil samples 30-40 cm; 60-70 cm and 90-100 cm deep were taken from five points in the studied area on 17 July 2001. The contaminants were determined by a small scale method which consists on extraction and clean-up steps combined into one step by transferring soil samples mixed with neutral alumina to a chromatographic column prepacked with neutral alumina and elution with hexane:dichloromethane (7:3 v:v). The eluate was concentrated and the analytes were quantified by gas chromatography with an electron-capture detector. p,p'-DDT at surface soil ranged from 3,800 to 7,300 mg kg(-1). 30-40 cm deep soil sample concentrations varied from 0.036 to 440 mg kg(-1) while 90-100 cm deep samples varied from 0.069 to 180 mg kg(-1). Volatilization is probably the main dissipation process. The p,p'-DDT is moving slowly downward in the soil profile, however, the levels of this contaminant are high enough to present risk to underground waters.     

Rapid resolution liquid chromatography-tandem mass spectrometry method for the determination of endocrine disrupting chemicals (EDCs), pharmaceuticals and personal care products (PPCPs) in wastewater irrigated soils

A multiresidue analytical method was developed for the determination of 9 endocrine disrupting chemicals (EDCs) and 19 pharmaceuticals and personal care products (PPCPs) including acidic and neutral pharmaceuticals in water and soil samples using rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS). Solid phase extraction (SPE), and ultrasonic extraction combined with silica gel purification were applied as pretreatment methods for water and soil samples, respectively. The extracts of the EDCs and PPCPs in water and soil samples were then analyzed by RRLC-MS/MS in electrospray ionization (ESI) mode in three independent runs. The chromatographic mobile phases consisted of Milli-Q water and acetonitrile for EDCs and neutral pharmaceuticals, and Milli-Q water containing 0.01 % acetic acid (v/v) and acetonitrile: methanol (1:1, v/v) for acidic pharmaceuticals at a flow rate of 0.3 mL/min. Most of the target compounds exhibited signal suppression due to matrix effects. Measures taken to reduce matrix effects included use of isotope-labeled internal standards, and application of matrix-match calibration curves in the RRLC-MS/MS analyses. The limits of quantitation ranged between 0.15 and 14.08 ng/L for water samples and between 0.06 and 10.64 ng/g for solid samples. The recoveries for the target analytes ranged from 62 to 208 % in water samples and 43 to 177 % in solid samples, with majority of the target compounds having recoveries ranging between 70–120 %. Precision, expressed as the relative standard deviation (RSD), was obtained less than 7.6 and 20.5 % for repeatability and reproducibility, respectively. The established method was successfully applied to the water and soil samples from four irrigated plots in Guangzhou. Six compounds namely bisphenol-A, 4-nonylphenol, triclosan, triclocarban, salicylic acid and clofibric acid were detected in the 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.     

Bioassay for determining sensitivity to sulfosulfuron on seven plant species

This study presents a bioassay procedure, based on the root and shoot growth parameters, for the determination of the herbicide sulfosulfuron (1-(4,6 dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-ylsulfonil)urea) sensitivity on seven vegetal species. Plant response to sulfosulfuron was calculated with the equations fitted to the root growth data as a function of the logarithm of the herbicide concentration by non-linear regression and was used to calculate the doses for 10, 30 and 50% inhibition of root growth (EC10, EC30 and EC50). The results indicate that the phytotoxic effect of sulfosulfuron in all the species assayed followed the order: flax > maize > onion > vetch > lepidium sativum > tomato > barley. These species showed phytotoxicity at low levels of sulfosulfuron and flax appeared to be the most susceptible species to sulfosulfuron (0.001 mg/L).     

Pharmaceutical and personal care products in groundwater, subsurface drainage, soil, and wheat grain, following a high single application of municipal biosolids to a field

Dewatered municipal biosolids (DMBs) were applied to a field at a rate of ~22 Mg dw ha(-1) in October 2008. Pharmaceuticals and personal care products (PPCPs) were monitored in groundwater, tile drainage, soil, DMB aggregates incorporated into the soil post-land application, and in the grain of wheat grown on the field for a period of ~1 year following application. Over 80 PPCPs were analyzed in the source DMB. PPCPs selected for in-depth monitoring included: antibiotics (tetracyclines, fluoroquinolones), bacteriocides (triclosan, triclocarban), beta-blockers (atenolol, propranolol, metaprolol), antidepressants (fluoxetine, citalopram, venlafaxine, sertraline), antifungals (miconazole), analgesics (acetaminophen, ibuprofen) and anticonvulsants (carbamazepine). PPCPs in tile were observed twice, ~3 weeks and 2 months post-application. Of all PPCPs measured in tile drainage, only carbamazepine, ibuprofen, acetaminophen, triclosan, triclocarban, venlafaxine, and citalopram were detected (5-74 ng L(-1)). PPCPs were not detected in groundwater >2 m depth below the soil surface, and concentrations above detection limits at 2 m depth were only observed once just after the first rain event post-application. In groundwater, all compounds found in tile, except carbamazepine, acetaminophen and citalopram, were detected (10-19 ng L(-1)). PPCPs were detected in DMB aggregates incorporated in soil up to 1 year post-application, with miconazole and fluoxetine having the lowest percent reductions over 1 year (~50%). For several compounds in these aggregates, concentration declines were of exponential decay form. No PPCPs were detected in the grain of wheat planted post-application on the field. No PPCPs were ever detected in water, soil or grain samples from the reference plot, where no DMB was applied.     

Mobility and plant availability of risk elements in soil after long-term application of farmyard manure

Crop rotation long-term field experiments were established in 1955 and 1956 at three locations in the Czech Republic (?áslav, Ivanovice, and Lukavec) differing in their climatic and soil physicochemical properties. The effect of long-term application of farmyard manure and farmyard manure + NPK treatments on plant-available, easily mobilizable, potentially mobilizable, and pseudo-total contents of arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) contents in soils (in 2013) as well as the uptake of these elements by winter wheat (Triticum aestivum L.) grain and straw were analyzed in the two following seasons: 2012 and 2013. The treatments resulted in increasing the soil pH level when compared to the control, but the cation exchange capacity remained unchanged. Although all fertilizers were applied for six decades, the pseudo-total concentration elements in both the soil and wheat plants stayed far below those of the Czech and European threshold limits for agricultural soils and cereals for human nutrition and feedstuff. Although the mobile pools of As, Cu, and Zn were slightly changed at the treated soils, these changes were not related to the element uptake by the wheat plants. Moreover, the effect of the location and growing season was more decisive for the differences in soil and plant element contents than for the individual treatments. Thus, the long-term application of farmyard manure did not result in any substantial change in risk element contents in both soils and winter wheat plants.     

Impacts of ozone on the growth and yield of field-grown winter wheat

Seed of winter wheat (Triticum aestivum L. cv Riband) was sown on 29 August 1992 in eight field plots. Four plots were exposed to elevated ozone (O(3)) concentrations on 16 days between 29 August and 2 October 1992, for 6 h day(-1), and on 27 days between 29 March and 24 August 1993, for 7 h day(-1). Mean daily O(3) concentrations were approximately 30 and 80 nmol mol(-1) in ambient and fumigated plots, respectively. Plants were sampled on 5 November (1992), 14 January, 16 February, 1 April, 25 May, 23 June and 24 August (1993). No visible symptoms of O(3) damage or premature senescence were observed at any time over the course of the experiment. Exposure to elevated O(3) decreased the above ground biomass by reducing plant density and individual plant relative growth rate. However, there was no significant influence of the pollutant on the growth of the root relative to the shoot. Assessment of yield characteristics at the final harvest revealed an O(3)-induced decrease in the number of grains per ear, as a result of fewer grains per spikelet and an increase in the number of infertile florets per spikelet. No significant effects of the pollutant on the number of ears per plant, spikelets per ear, or 1000 grain weight were found. As a result of the combined effects on the number of grains per ear and the decrease in plant density and growth rate, O(3) exposure reduced grain and straw yields (tonnes ha(-1)) by 13 and 8%, respectively. However, no significant change in the partitioning of dry matter between the grain and the straw was observed in fumigated plots. The findings are discussed within the context of United Nation Economic Commission for Europe critical level guidelines for the protection of crop yields, in relation to their application to winter-sown crops.     

Transfer of cadmium, lead, and zinc from industrially contaminated soil to crop plants: a field study

The documeneed adverse health effects of soil Cd and Pb have led to public concern over soil contamination with metals. A 4-year field experiment was conducted to study the transfer of Cd, Pb, and Zn from soil contaminated by smelter flue-dust to crop plants grown in a rotation. The soil was amended with Pb?Zn smelter flue-dust (2-66.8 kg per 10 m(2) plot) to simulate the long-term effect that the smelting of non-ferrous metal ore has on arable soils. The treated soil became strongly contaminated with metals (Cd 3.2-106 mg/kg, Pb 146-3452 mg/kg, Zn 465-11 375 mg/kg). Concentrations of Cd, Pb, and Zn in barley grain, barley straw meadow bluegrass, red clover, and potatoes were generally low. The highest metal concentrations were found in potato tubers (intact), meadow bluegrass, and barley straw. The observed reduction in crop yield was probably the result of possible nutrient imbalances rather than of metal (Zn, Cu) phytotoxicities. Zn and Cd uptake by the plants can be described by the saturation (plateau) model (y = ax(b), b < 1). The relationship between Pb in the soil and plants was linear with an extremely low slope (0.0001-0.0003). No excessive dietary intake of Cd is expected when Cd concentrations in barley grain and potato tubers grown on the contaminated soil are not higher than 0.6 and 1.0 mg/kg, respectively. Based on the risk analysis and taking into account the saturation model of the soil-plant metal relationship, it was concluded that, under the conditions of this experiment (neutral soil pH), soil with Cd concentrations of up to 30 mg/kg is still safe for production of these crop plants.     

Bioassay for Determining Sensitivity to Sulfosulfuron on Seven Plant Species

This study presents a bioassay procedure, based on the root and shoot growth parameters, for the determination of the herbicide sulfosulfuron (1-(4,6 dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-ylsulfonil)urea) sensitivity on seven vegetal species. Plant response to sulfosulfuron was calculated with the equations fitted to the root growth data as a function of the logarithm of the herbicide concentration by non-linear regression and was used to calculate the doses for 10, 30 and 50% inhibition of root growth (EC₁₀, EC₃₀ and EC₅₀). The results indicate that the phytotoxic effect of sulfosulfuron in all the species assayed followed the order: flax > maize > onion > vetch > lepidium sativum > tomato > barley. These species showed phytotoxicity at low levels of sulfosulfuron and flax appeared to be the most susceptible species to sulfosulfuron (0.001 mg/L).     

Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Evaluation of soil characteristics potentially affecting arsenic concentration in paddy rice (Oryza sativa L.)

Paddy rice may contribute considerably to the human intake of As. The knowledge of soil characteristics affecting the As content of the rice plant enables the development of agricultural measures for controlling As uptake.During field surveys in 2004 and 2006, plant samples from 68 fields (Italy, Po-area) revealed markedly differing As concentration in polished rice. The soil factors total As_{(aqua regia)}, pH, grain size fractions, total C, plant available P_(CAL), poorly crystalline Fe_(oxal.) and plant available Si_(Na-acetate) content that potentially affect As content of rice were determined.A multiple linear regression analysis showed a significant positive influence of the total As_{(aqua regia)} and plant available P_(CAL) content and a negative influence of the poorly crystalline Fe_(oxal.) content of the soil on the As content in polished rice and rice straw.Si concentration in rice straw varied widely and was negatively related to As content in straw and polished rice.