Study of atrazine degradation in soil from Kenyan sugarcane-cultivated fields in controlled laboratory conditions

A study to compare the extent of atrazine mineralization in soils from Kenyan sugarcane-cultivated fields with and without history of atrazine use was carried out in the laboratory under controlled conditions. The study was testing the hypothesis that repeated atrazine application to soil will not result in enhanced atrazine mineralization. The study was carried out with ¹⁴C-uniformly ring-labeled atrazine in a laboratory under controlled conditions. Atrazine mineralization to ¹⁴CO₂ in soil with no history of atrazine use was negligible (0.16%) after 163 days of soil incubation. The three metabolites hydroxyatrazine, desisopropylatrazine, and desethylatrazine in the proportion of 17.7%, 1.3%, and 2.6%, respectively, were in the soil after 75 days. In the soil from the sugarcane-cultivated field with history of atrazine use, atrazine mineralization was 89.9% after 98 days. The same soil, amended with mature compost, showed a lag phase of eight days before rapid atrazine mineralization was observed.     

Adsorption distribution impact on preferential transport within horizontal flow constructed wetland (HFCW)

Predicting preferential water flow and solute transport in soils is in the interest of scientists and engineers in the fields of agricultural soil, forest hydrology, soil physics and wastewater treatment by constructed wetland. In artificial wetlands, any preferential pathway induces an insufficient residence time of pollutants in the soil, making an incomplete and unfinished biodegradation process, a wrong evaluation of the hydraulic residence time of the system which would hinder its management in a complete system with several entities of treatment and a non-homogeneous growth of the biofilm in the solid filter mass. This paper is a contribution in tracer experiment data analysis within a horizontal flow constructed wetland built in a storm water basin. A two-dimensional numerical model was used to simulate flow and reactive solute transport. The flow model was successfully calibrated in very dry soil conditions. The adsorption profiles used in the reactive transport modeling are those of five molecules: metolachlor, atrazine, deethylatrazine (DEA), deisopropylatrazine (DIA), and hydroxyatrazine (HA). We show that the adsorption distribution is an internal factor of soil which is responsible to the “preferential” pathway transport in a homogeneous gravel texture. The mean residence time of pollutants within the filter is strongly correlated with the average value of the adsorption coefficient. Moreover, we note a lack of significant impact of the heterogeneity of the medium on the statistical moments of breakthrough curve. It appears that a uni-modal breakthrough curve is not significant to the absence of preferential flow in the medium and at least a two-dimensional display can provide sufficient evidence on the presence or absence of preferential pathways. Finally, using a PLS regression, it is possible to perfectly discriminate the number of peaks of concentration and the asymmetry of the breakthrough curve.     

Aluminium in tea plantations: mobility in soils and plants, and the influence of nitrogen fertilization

The levels of extractable aluminum (Al) in soils of tea plantations, Al concentrations in tea leaves and the impact of nitrogen fertilization on these two parameters were investigated. In addition, the properties of soils from tea plantations were compared to those from soils of adjacent non-tea fields to evaluate the effect of land use conversion (from non-tea soils to tea soils). Exchangeable Al (extracted in 1 mol l⁻¹ KCl) ranged from 0.03 to 7.32 cmol_c kg⁻¹ in 94 tea fields and decreased rapidly with increasing soil pH. In comparison with non-tea soils, tea soils had a significantly lower pH and exchangeable Mg²⁺ concentration but higher organic matter contents and exchangeable K⁺ concentration. Contents of extractable Al were not different (P > 0.05) between these two soils. The concentrations of Al in mature tea leaves correlated significantly with exchangeable Al in soil samples taken at a depth of 20–40 cm and with exchangeable Al saturations in soil sampled at␣depths of 0–20 and 20–40 cm. In the pot experiment, nitrogen fertilization significantly increased extractable Al levels but decreased soil pH and the levels of exchangeable base cations. Nevertheless, the levels of Al in mature leaves and young shoots were significantly reduced by the application of large amounts of N fertilizer.     

Quantification and fractionation of mercury in soils from the Chatian mercury mining deposit,southwestern China

Contents of total Hg and Hg fraction, organic matter, pH, grain size and chemical composition were measured to investigate the pollution characteristics and binding behavior of Hg in soils collected from the Chatian Hg mining deposit (CMD), southwestern China. The average concentration of Hg concentration in the CMD soils was 155 and 1,315 times higher than that in control soils and Chinese soils, respectively, suggesting that the CMD soils were heavily contaminated by the element. The finding was confirmed by Müller geoaccumulation index assessment with 75% very seriously polluted, 6.25% highly to very highly polluted and 18.75% moderately to highly polluted. Hg sources in the region were natural and anthropogenic: in addition to the pedogenic process and original geochemical situation, human mining–refining activities have also seriously impacted the redistribution of Hg in soils, especially in paddy soils. Based on the BCR protocol, soil Hg was divided into exchangeable (EXC), amorphous Fe–Mn oxides (AFe–MnOX), organic-crystalline iron oxides (OM-CFe) and residual (RES) fraction. The average percentage of the four fractions in the CMD followed the trend: RES (85.77%) > OM-CFe (12.44%) > AFe–MnOX (0.93%) ≥ EXC (0.86%), suggesting that the majority proportion of soil Hg in the study area remained of residual form inside the soil mineral matrix. However, their concentrations and percentages significantly varied among different locations and land use types. Soil physico-chemical parameters were key factors affecting the presence of Hg fraction. Generally, Hg fraction concentrations were positively correlated with the sand contents and soil pH values, which was presumably due to the basic anthropogenic input of Hg-containing materials and their similarity to sand in physical characteristics. However, organic matter caused adsorption–fixation and reduction–volatilization to coexist, which had opposite effects on Hg concentrations in soil, consequently exhibiting its dual nature.     

Chemical availability of arsenic and antimony in industrial soils

Total concentrations and extractable fractionations of As and Sb were determined in soil samples from former mining sites in Scotland and Italy. Pseudo-total levels of As and Sb in the sample were between 50–17,428 mg/kg and 10–1,187 mg/kg (Scotland), and 16–691 mg/kg and 1.63–11.44 mg/kg (Italy). Between 0.001–0.63% and <0.001−8.82% of the total soil As and Sb, were extractable using, a single extraction bioavailability estimate. Data from an As-specific extraction procedure revealed that up to 60% of As was associated to amorphous Fe-Al oxyhydroxide phase in all soils. A non-specific-sequential extraction test also showed As to be strongly associated with Fe (and Al) oxyhydroxides at both locations. In the case of Sb, in addition to the crystalline Fe-oxide bound Sb the Al-silicate phase also appeared to be significant. At both sites Sb appears to be chemically more accessible than As with consistent availability despite the varied origin and host soil properties.     

Environmental fate of pesticides used in Australian viticulture V. Behaviour of atrazine in the soils of the south Australian Riverland

The transport of the s‐triazine herbicide, atrazine, through the red, calcareous earth soils of the South Australian Riverland was investigated. Small, undisturbed soil cores were extracted from the inter‐row topsoil of a vineyard adjacent to the River Murray, approximately 10 km south‐west of Overland Corner, South Australia. The vines were grown in a deep (1–4 m) reddish brown, strongly alkaline, sandy loam with a low organic carbon content (<2%). Atrazine concentrations in the leachate were dependent on application rate and soil type. High application rates on subsoil gave high rates of leaching for a longer time compared to the same application rate on topsoil and/or lower application rates on either topsoil or subsoil. Overall, 37–65% of the applied atrazine was detected in the leachate from subsoil cores, 14–25% in topsoil core leachates. Small amounts of atrazine (< 10% of applied dose) were found only in the top 2 cm of the core profiles. The results suggest that this herbicide is somewhat mobile in such strongly alkaline, sandy loam soils and that the irrigated soils of this region are likely to be prone to leaching of atrazine, and therefore that groundwater supplies in this area may be at risk of contamination through use of triazine herbicides.     

Distribution and mobility of metals in agricultural soils near a copper smelter in South China

The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were heavily affected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin. Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the residual and NH₂OH HCl extractable fractions. In contrast, Cd was predominantly associated with the MgCl₂ extractable fraction. A large proportion of Cu was bound to the acidic H₂O₂ extractable fractions, while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water extraction using a modification of Tessier’s procedure, and the order of mobility was Zn > Cd > Cu  > Pb.     

Changes in chemical forms of lead in temperate and semiarid soils in sterile and unsterile conditions

Sequential extraction has been used as a suitable method for fractionation of chemical forms of trace elements and study of their plant availability. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The chemical forms of Pb in the Pb(NO₃)₂-treated (400 μg Pb g⁻¹) soils have been studied in solid state incubation (FC) at 27°C in sterile and unsterile conditions. After 20 min and 3600 h a sequential extraction scheme was also used to fractionate Pb of incubated samples into soluble-exchangeable (Sol-Exch), carbonates associated (ACar), organic matter associated (AOM), Mn oxide associated (AMnOx), Fe oxide associated (AFeOx), and residual (Res) forms. Temperate soil samples had higher clay content, cation exchange capacity (CEC), dichromate oxidable organic carbon (OC), total Kjeldahl-nitrogen (TN), biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate (ECC), available P and K. Soil lead fractionation revealed that in both groups of soils Pb largely changed to exchangeable, carbonates associated and organic associated forms after 20 min. The chemical forms of Pb differed widely among soils after 3600-h incubation. The conversion rate of Pb from more available forms to less available forms was higher in temperate soils with higher Fe–Mn oxides and OM contents compared to semiarid soils. In temperate soils after 3600-h incubation, greater content of Pb was observed in Res (68%), AOM (14%), ACar (7%), and AMnOx (5%) fractions. However, in semiarid soils greater content of Pb was observed in Res (61%), ACar (16%), Sol-Exch (8%), and AOM (8%) fractions. The sum of AMnOx and AFeOx chemical forms for Pb in semiarid soils compared to temperate soils was lower. It was only 7% against 9% in temperate soils. Soil microorganisms in unsterile soils had significant effect on AOM, AFeOx and Res fractions of Pb. They not only increased AOM and AFeOx fractions of Pb in soils but also decreased Res fraction of Pb significantly.     

Isolation and characterization of an Arthrobacter sp. strain HB-5 that transforms atrazine

A bacterial strain (HB-5) capable of utilizing atrazine as sole carbon and nitrogen source for growth was isolated from an industrial wastewater sample by enrichment culture. The isolate was identified as Arthrobacter sp. according to its phenotypic features, physiologic and biochemical characteristics, and phylogenetic analysis. The strain exhibited faster atrazine degradation rates in atrazine-containing mineral media than the well-characterized atrazine-degrading bacteria Pseudomonas sp. ADP. The broad optimum pH and temperature ranges observed for strain HB-5 indicate that it has potential for remediation of atrazine-contaminated sites. Strain HB-5 first metabolizes atrazine to yield hydroxyatrazine. Then, the bacterium metabolizes hydroxyatrazine to cyanuric acid, but could not mineralize atrazine.     

Influence of humic acid on the sorption of uranium(IV) to kaolin

Safety assessments for radioactive waste disposal require estimations of the migration of radionuclides in soils. The influence of humic acid (HA) on the sorption of uranium in its +4 oxidation state to kaolin has been examined from pH 4 to 8, with HA concentrations of 15–200 ppm. In the absence of HA, 20–40% of the U(IV) was in solution, with more sorption occurring at higher pH. The presence of HA solubilised up to 90% of the uranium with higher solubilities at higher HA concentrations and higher pH values. Uranium sorption was mapped against HA sorption, and it was found that there was a lower level of U(IV) sorption than can be accounted for by just measuring HA sorption. However, this effect got less marked as the pH rose. Sensitivity analysis indicated that the fraction of surface-bound HA is the controlling parameter for modelling in these systems.     

Selenium Distribution in Topsoils and Plants of a Semi-arid Mediterranean Environment

Selenium was determined from 25 topsoils and 25 plants in the semi-arid Central Spain where large extents of soils are developed on evaporitic materials. Some species of vegetation associated with them are of the genera Astragalus, Salsola, Mercurialis, Phlomis, Thymus and Atriplex. Total selenium in soils was determined and its bioavailability assessed by chemical sequential fractionation. Se content in soils was adequate (in the range 0.17–0.39 mg kg⁻¹) or large (in the range 0.50–4.38 mg kg⁻¹) and appeared in highly and/or potentially available forms. Several plant species showed high Se levels (in the range 5–14.3 mg kg⁻¹), which can be a potential risk of toxicity to animals. Data obtained from the study area can be used as a guide to the range of values in soils and plants of the European Mediterranean area that are relatively unpolluted from industrial sources, allowing comparison with more polluted areas.     

Atrazine contamination in agricultural soils from the Yangtze River Delta of China and associated health risks

Atrazine is one of the most widely applied and persistent herbicides in the world. In view of limited information on the regional contamination of atrazine in soils in China, this study investigated the spatial distribution and environmental impacts of atrazine in agricultural soils collected from the Yangtze River Delta (YRD) as an illustrative analysis of rapidly developing regions in the country. The results showed that the concentrations of atrazine in the YRD agricultural soils ranged from <1.0 to 113 ng/g dry weight, with a mean of 5.7 ng/g, and a detection rate of 57.7 % in soils. Pesticide factory might be a major source for the elevated levels of atrazine in Zhejiang Province. The contamination of atrazine was closely associated with land use types. The concentrations and detection rates of atrazine were higher in corn fields and mulberry fields than in rice paddy fields. There was no significant difference in compositions of soil microbial phospholipids fatty acids among the areas with different atrazine levels. Positive relationship (R = 0.417, p < 0.05, n = 30) was observed between atrazine and total microbial biomass. However, other factors, such as soil type and land management practice, might have stronger influences on soil microbial communities. Human health risks via exposure to atrazine in soils were estimated according to the methods recommended by the US EPA. Atrazine by itself in all the soil samples imposed very low carcinogenic risks (<10^?6) and minimal non-cancer risks (hazard index <1) to adults and children.     

A pilot study on iodine in soils of Greater Kabul and Nangarhar provinces of Afghanistan

A robust and rapid methodology for the determination of iodine by inductively coupled plasma mass spectrometry in environmental samples is presented. Data were initially obtained for the validation of the analytical measurements, using 17 commercially available soil reference materials. The methodology was then tested on soil and water samples collected in Afghanistan where iodine deficiency and its effects are reportedly prevalent. Sample collections were conducted in Greater Kabul; the iodine in agricultural soils was determined to be in the range of 1.6–4.2 mg/kg and that in water drawn for drinking and irrigation was found to range from 9.9 to 22.7 μg/L. Samples were also collected in a second region, Nangarhar province, which is located to the east of Kabul, where goitres in the local population had been reported. The iodine content in soils and water at this location was 0.5–1.9 mg/kg and 5.4–9.4 μg/L, respectively. The organic content of soils in Kabul was found to be in the range of 1.9–4.2%; in Nangarhar, organic content ranged from 1.7 to 4.5%. All of the Afghan soils were slightly alkaline at pH 7.6–8.2.     

Bioaccessibility of arsenic in soils developed over Jurassic ironstones in eastern England

Jurassic ironstones outcropping over parts of eastern England give rise to soils with arsenic concentrations in excess of the UK soil guideline value of 20 mg kg⁻¹ for residential areas. Total arsenic concentrations were determined for 73 ironstone derived soils and bioaccessible arsenic determined using an in vitro physiologically based extraction test. The bioaccessible arsenic concentration for these soils was found to be well below the soil guideline value with a mean concentration of 4 mg kg⁻¹ and a range of 2–17 mg kg⁻¹. The bioaccessible fraction ranges from 1.2 to 33%. Data from a sequential extraction test based on the use of aqua regia as the main extractant is presented for a subset of 20 of the soils. Chemometric data reduction is used to demonstrate that the bioaccessible arsenic is mainly contained within calcium iron carbonate (sideritic) assemblages and only partially iron aluminosilicates, probably berthierine, and iron oxyhydroxide phases, probably goethite. It is suggested that the bulk of the non-bioaccessible arsenic is bound up with less reactive iron oxide phases.     

Environmental degradation of atrazine,linuron and fenitrothion in soil samples

The persistence of atrazine, linuron and fenitrothion in soil samples from an estuarine area (Ebro delta, Tarragona, Spain) has been studied. Soil samples from the top surface (10 cm) were collected during 1989–91, freeze‐dried, sieved through 200 μm, Soxhlet extracted with methanol, cleaned‐up with Florisil and analysed either by gas chromatography‐nitrogen phosphorus detection (GC‐NPD), in the case of atrazine and fenitrothion, or by liquid chromatography with diode array detection (LC‐DAD), for linuron. Confirmation of the samples analysed by GC‐NPD was carried out using GC‐mass spectrometric detection (MS) in the electron impact mode. The soil half lives obtained under the real environmental conditions have been calculated and the values obtained have been correlated with the physicochemical properties of each pesticide and the soil type. Degradation was affected by volatilization since temperatures in the area of study are relatively high, ca. 30°C, in the summer period. In the case of atrazine it has been shown that deethylatrazine is formed in all the samples studied..     

Fractionation and speciation of arsenic in fresh and combusted coal wastes from Yangquan, northern China

In this study, the content and speciation of arsenic in coal waste and gas condensates from coal waste fires were investigated, respectively, using the digestion and sequential extraction methods. The fresh and fired-coal waste samples were collected from Yangquan, which is one of the major coal production regions in northern China. High-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) was used to determine the concentrations of four major arsenic species [As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA)] in the extracts, while ICP-MS was used to measure total As content. Arsenic content in the investigated coal wastes and the condensate ranges between 23.3 and 69.3 mg/kg, which are higher than its reported average content in soils. Arsenic in coal waste exists primarily in the residual fraction; this is followed in decreasing order by the organic matter-bound, Fe–Mn oxides-bound, exchangeable, carbonates-bound, and water-soluble fractions. The high content of arsenic in the condensates indicates that combustion or spontaneous combustion is one of the major ways for arsenic release into the environment from coal waste. About 15% of the arsenic in the condensate sample is labile and can release into the environment under leaching processes. The water extractable arsenic (WEA) in the fresh coal waste, fired coal wastes, and the condensate varied between 14.6 and 341 μg/kg, with As(V) as the major species. Furthermore, both MMA and DMA were found in fresh coal wastes, fired coal wastes, and the condensate.     

阿特拉津在土壤中的降解途径及其对持留性的影响

通过田间和实验室试验，研究了除草剂阿特拉津在土壤中的降解代谢规律及其与土壤特性的关系。试验表明，阿特拉津施用后、在作物生长期内可降解９０％以上，土壤酸碱度对阿特拉津在土壤中的代谢有显著影响。在碱性土壤中阿特拉津主要经过微生物代谢而被降解；在酸性土壤中化学水解占优势地位。阿特拉津在强酸性土壤中的持留性（半衰期为６３ｄ）低于弱酸性土壤中的持留性（半衰期为８４ｄ），而在碱性土壤中由于较强的微生物降解作用，其持留性（半衰期为５１ｄ）最低。     

Evaluation of heavy metal contamination in Phaeozem of northeast China

Surface and profile Phaeozem soil samples from 31 locations affected by various anthropogenic activities such as mining, chemical manufacturing, traffic emission and pesticide application were collected in Heilongjiang Province and Jilin Province, northeast China. The range of total concentrations of four heavy metals Cd, Pb, Cu and Zn in the soil was 0.011–3.137, 10.31–62.34, 9.74–51.21 and 39.54–247.59 mg kg⁻¹, respectively, determined using the acidic digestion procedure. Four methods including single contamination evaluation, background concentration comparison, surface/subsurface concentration comparison and exchangeable fraction evaluation were used to evaluate the extent of metal contamination in Phaeozem. The results indicated that different activities increased the concentrations of the heavy metals in surface soils, where high concentrations of cadmium and lead were found close to chemical plants and in the suburbs of the investigated cities. The four methods showed a general trend of increased soil contamination with heavy metals. Cadmium was of the most concern compared with the other contaminated elements in the study area, due to the long-term phosphatic fertilizer utilization and industrial activities. The proper evaluation method for cadmium contamination was the background concentration comparison, while for zinc and copper was the single contaminative index evaluation. Cadmium and lead could be the potential environmental risk in the Phaeozem area based on the different evaluations.     

Removal of atrazine from river waters by indigenous microorganisms

We report the first data for atrazine removal in low-turbidity freshwaters. Atrazine is a globally applied herbicide, contamination by which may lead to direct and indirect ecotoxicological impacts. Although a common contaminant of surface waters, microbial biodegradation of atrazine in this environment has been little studied, with most work focused on soils by means of selected, atrazine-degrading bacteria-enriched cultures. Here, we measured atrazine removal from river water using a batch incubation system designed to represent environmental conditions, with water from two contrasting UK rivers, the Tamar and Mersey. Atrazine and bacterial inocula prepared from the source water were added to cleaned river water for 21-day incubations that were analysed directly by electrospray ionisation-mass spectrometry. The experimental approach was validated using peptides of different molecular mass. Results show that atrazine concentrations decreased by 11% over 21 days in Tamar samples, a rural catchment with low population density, when atrazine was the only substrate added. In contrast no removal was evident in Mersey samples, an urban catchment with high population density. When a tripeptide was added as a co-substrate, atrazine removal in the Tamar water remained at 11% while that for the Mersey water increased from 0 to 37%. Although degradation of atrazine in aerobic freshwaters is predicted according to its chemical structure, our data suggest that the composition of the bacterial population determines whether removal occurs under these conditions and at these environmentally realistic concentrations.     

阿特拉津对不同肥力土壤磷酸酶的影响

通过室内恒温培养法，研究除草剂阿特拉津对4种长期定位施肥处理下的土壤的磷酸酶活性的影响。试验结果表明，在阿特拉津质量分数不同和处理时间长短不同的情况下，阿特拉津对土壤磷酸酶的活性既有激活作用又有抑制作用。在试验过程中，4种不同肥力的土壤其磷酸酶活性随着处理时间的延续而呈现出“降低→升高→降低→升高”的消长趋势。不同阿特拉津质量分数对磷酸酶的影响没有规律，同一质量分数处理既有激活作用，也有抑制作用。在4种不同肥力的土壤中，磷酸酶活性最高的是以氮、磷、钾无机肥配合有机肥施用的土壤。