Factors affecting metribuzin retention in Algerian soils and assessment of the risks of contamination

Metribuzin is a widely used herbicide around the world but it could lead to soil and water contamination. Metribuzin retention on a silty–clay agricultural soil of Algeria was studied in laboratory batch experiments to assess the contamination risk of the groundwater. Factors conditioning the fate of metribuzin were investigated: soil nature, metribuzin formulation, NPK fertilizer, and soil pH. Freundlich sorption isotherms gave the coefficients K _F between 1.2 and 4.9 and 1/n _a between 0.52 and 0.93. The adsorption is directly dependent on organic and clay soil contents. Formulated metribuzin (Metriphar) reduces the adsorption (K _F?=?1.25) compared to pure metribuzin (K _F?=?2.81). The addition of an NPK fertilizer decreases the soil pH (6.67 for the soil without fertilizer and 5.86 for 2 % of fertilizer) and increases metribuzin adsorption (K _F is 4.83 for 2 % of fertilizer). The pH effect on the adsorption is corroborated in experiments changing the soil pH between 5 (K _F is 4.17) and 8 (K _F is 1.57) under controlled conditions. Desorption isotherms show a hysteresis and only 30 to 40 % of the initially adsorbed metribuzin is released. The estimated GUS index is ≥2.8 for a DT50?≥?30 days. K _F values and the hysteresis show that metribuzin is little but strongly retained on the soil. Formulated metribuzin and addition of fertilizer affect the retention. However, the GUS index indicates a high mobility and a significant risk of leaching. The most appropriate risk management measure would be an important increase in organic matter content of the soil by addition of organic amendments.     

The mobility of heavy metals in soils in the Krušné Hory and Slavkovský Les mountains

In the North Bohemian forest soils the total content and EDTA, HAc and H₂O-extractable portions of Cr, Co, Ni, Cu, Pb and Zn were investigated. Increased concentration of Pb in topsoils, in comparison with subsoils, is the result of air pollution. The extractable portion of all studied heavy metals is higher in topsoil than in subsoil.     

Total concentrations, fractionation and mobility of heavy metals in soils of urban area of Guwahati, India

This work describes the results of assessment of the heavy metals, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn in urban soil of Guwahati City, India from 31 sites of five different land use types covering residential, commercial, industrial, public utilities, and roadside. Sequential extraction procedure was used to evaluate the relative distribution of the eight metals in exchangeable, carbonate, reducible (Fe?CMn oxide), organic and sulfide, and residual fractions. Of the eight metals, Cd and Co occur in lower concentrations (Cd <?< Co) in all types of land, and concentration variation from one type of land use to another is not much significant for both the metals. Ni presence is more than Co, and the concentrations show some variation depending on land use status. Average Cr and Cu concentrations are ??100?mg/kg, but Cr has a significantly higher presence in industrial land use. The results are similar in case of Pb. The two metals, Mn and Zn have domination over the other metals, and the values are ??300?mg/kg. Industrial and roadside soil contains much more Mn, while commercial soil is most enriched with Zn. Of the metals, Ni has the largest proportion (~42%) bound to the exchangeable fraction and Co, Cr, and Pb also have appreciable proportion bound to the same fraction. A significant amount of Co is associated with carbonates. The reducible fraction has bound considerable quantity of Mn and Zn, while most of Cu is associated with the organic and sulfide fraction. Both Cd and Pb are dominantly associated with the residual fraction. Computation of the mobility factor of the metals indicates Mn to be the most mobile metal present in the soil samples.     

A field screening test for the assessment of concentrations and mobility of potentially toxic elements in soils: a case study on urban soils from Rome and Novi Sad

The increasing demand for environmental pollution control results in the development and use of new procedures for the determination of dangerous chemicals. Simple screening methods, which can be used directly in the field for a preliminary assessment of soil contamination, seem to be extremely advantageous. In our laboratory, we developed and optimized a rapid test for a preliminary evaluation of both the concentration and the mobility of some potentially toxic metals in soils. This screening test consists of a single extraction of the soil sample with a buffer solution, followed by the titration of the extracted solution with dithizone to determine the contents of bi-valent heavy metals (such as Pb, Cu, Zn, and Cd). This screening method was then directly applied in the field during the sampling campaign in the framework of an Italian–Serbian collaborative project, finalized in the study of metal availability in soils. The results obtained in the field with the rapid test were compared with those obtained in the laboratory following the conventional procedure commonly used to evaluate metal bioavailability (diethylenetriaminepentaacetic extraction). Moreover, selected samples were analyzed sequentially in the laboratory using the standardized BCR three-step sequential extraction procedure. The screening test gave results conceptually in good agreement with those obtained via the BCR procedure. These preliminary data show that the proposed screening test is a reliable method for the preliminary rapid evaluation of metal total concentrations and of potential metal mobility in soils, supporting sampling activities directly in the field.     

Use of sequential extraction to assess the influence of sewage sludge amendment on metal mobility in Chilean soils

In Chile, the increasing number of plants for the treatment of wastewater has brought about an increase in the generation of sludge. One way of sludge disposal is its application on land; this, however involves some problems, some of them being heavy metal accumulation and the increase in organic matter and other components from sewage sludge which may change the distribution and mobility of heavy metals. The purpose of the present study was to determine the effect of sewage sludge application on the distribution of Cr, Ni, Cu, Zn and Pb in agricultural soils in Chile. Three different soils, two Mollisols and one Alfisol, were sampled from an agricultural area in Central Chile. The soils were treated with sewage sludge at the rates of 0 and 30 ton ha(-1), and were incubated at 25 degrees C for 45 days. Before and after incubation, the soils were sequentially extracted to obtain labile (exchangeable and sodium acetate-soluble), potentially labile (soluble in moderately reducing conditions, K4P2O7-soluble and soluble in reducing conditions) and inert (soluble in strong acid oxidizing conditions) fractions. A two-level factored design was used to assess the effect of sludge application rate, incubation time and their interaction on the mobility of the elements under study. Among the metals determined in the sludge, zinc has the highest concentration. However, with the exception of Ni, the total content of metals was lower than the recommended limit values in sewage sludge as stated by Chilean regulations. Although 23% of zinc in sludge was in more mobile forms, the residual fraction of all metals was the predominant form in soils and sludge. The content of zinc only was significantly increased in two of the soils by sewage sludge application. On the other hand, with the exception of copper, the metals were redistributed in the first four fractions of amended soils. The effect of sludge application rate, incubation time and their interaction depended on the metal or soil type. In most cases an increase in more mobile forms of metals in soils was observed as the final effect.     

Availability and mobility of heavy metal fractions related to the characteristics of the coastal soils developed from alluvial deposits

The availability of the five chemical fractions, i.e., exchangeable (F1), carbonate-bound (F2), Fe/Mn oxide-combined (F3), organic matter-complexed (F4), residual (F5), of three heavy metals (Cu, Zn, and Cd), has been investigated by way of a sequential extraction technique based on the characteristics of the coastal soils developed from alluvial deposits, in order to analyze the relationship of the formation and development of coastal soils. The results showed that F1 and F5 of Cu, Zn, and Cd accounted dominantly for 9.11%, 2.74%, and 20.37%, and for 39.49%, 45.18%, and 32.43% of total heavy metal contents, respectively, indicating the order of availability and mobility: Cd > Cu > Zn. F2, F3, and F4 of HMs also featured prominently in the behaviors of heavy metals. Random measurement errors from both sampling and analysis were demonstrated by SAX to be well within the control target of 20% and, therefore, of no impediment to the geochemical interpretation of the data. Significant positive correlation was found between certain fractions of heavy metals and some soil properties. Some negative correlation was also found. The findings were helpful to the soil remediation, fertility adjustment, and plant cultivation.     

Pollution in the urban soils of Lianyungang,China, evaluated using a pollution index,mobility of heavy metals,and enzymatic activities

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.     

Application of laser-based ion mobility (IM) spectrometry for the analysis of polycyclic aromatic compounds (PAC) and petroleum products in soils

The capability of laser-based IM spectrometry to detect PAC and petroleum products (oils) in model matrices, laboratory reference (LR) materials and in real-world contaminated soil samples was demonstrated. Quantitative IM investigations of PAC-doped PVC films yielded detection limits in the ppm range for single PAC. The potential of IM spectrometry for in situ analysis was demonstrated by the analysis of PAC-containing certified reference (CR) material, and of petroleum product-containing LR materials and real-world soil samples. The calibration of IM signals obtained from oil-doped LR materials was also possible, and detection of oils with concentrations below 100 mg kg(-1) was achieved. The in situ analysis of real-world contaminated soils with the IM and LIF techniques was in good accordance with ex situ reference investigations.     

Pollution, fractionation, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils from a Pb/Zn mining area

This study was conducted to investigate the pollution load index, fraction distributions, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils collected from a Pb/Zn mine in Chenzhou City, China. The samples were analyzed using Leleyter and Probst’s sequential extraction procedures. Total metal concentrations including Pb, Cd, Cu, and Zn exceeded the maximum permissible limits for soils set by the Ministry of Environmental Protection of China, and the order of the pollution index was Cd > Zn > Pb > Cu, indicating that the soils from both sites seriously suffered from heavy metal pollution, especially Cd. The sums of metal fractions were in agreement with the total contents of heavy metals. However, there were significant differences in fraction distributions of heavy metals in garden and paddy soils. The residual fractions of heavy metals were the predominant form with 43.0% for Pb, 32.3% for Cd, 33.5% for Cu, and 44.2% for Zn in garden soil, while 51.6% for Pb, 40.4% for Cd, 40.3% for Cu, and 40.9% for Zn in paddy soil. Furthermore, the proportions of water-soluble and exchangeable fractions extracted by the selected analytical methods were the lowest among all fractions. On the basis of the speciation of heavy metals, the mobility factor values of heavy metals have the following order: Cd (25.2–19.8%) > Cu (22.6–6.3%) > Zn (9.6–6.0%) > Pb (6.7–2.5%) in both contaminated soils.     

Perchlorate contamination of groundwater from fireworks manufacturing area in South India

Perchlorate contamination was investigated in groundwater and surface water from Sivakasi and Madurai in the Tamil Nadu State of South India. Sensitive determination of perchlorate (LOQ?=?0.005 μg/L) was achieved by large-volume (500 μL) injection ion chromatography coupled with tandem mass spectrometry. Concentrations of perchlorate were <0.005–7,690 μg/L in groundwater (n?=?60), <0.005–30.2 μg/L in surface water (n?=?11), and 0.063–0.393 μg/L in tap water (n?=?3). Levels in groundwater were significantly higher in the fireworks factory area than in the other locations, indicating that the fireworks and safety match industries are principal sources of perchlorate pollution. This is the first study that reports the contamination status of perchlorate in this area and reveals firework manufacture to be the pollution source. Since perchlorate levels in 17 out of 57 groundwater samples from Sivakasi, and none from Madurai, exceeded the drinking water guideline level proposed by USEPA (15 μg/L), further investigation on human health is warranted.     

高氯酸铁可见分光光度法测定水中叠氮化物研究

基于Fe³⁺显色技术,建立了测定地表水、地下水、生活污水和工业废水中叠氮化物的高氯酸铁分光光度法。研究结果表明:N₃^-与Fe³⁺反应生成的棕红色络合物的特征吸收峰为454 nm;氨基磺酸铵可有效掩蔽NO₂^-的干扰,蒸馏能消除色度、CN^-、SCN^-硫化物等对测定的影响;当取样体积为150 mL、蒸馏定容体积为100 mL、使用10 mm比色皿时,方法检出限为0.08 mg/L(以N₃^-计),测定下限为0.32 mg/L;平均回收率为88.0%¹04%,相对标准偏差(n=6)为0.3%～5.6%。对实际工业废水样品进行了测定,结果为1.37 mg/L。该方法准确度高、精密度好、操作简单,能够满足水污染物排放标准中叠氮化物的测定要求。     

超声提取-离子色谱法测定常见土壤中的高氯酸盐

建立了测定土壤中高氯酸盐的离子色谱法,通过前处理条件优化和色谱条件优化形成准确高效的测定方法,并采集实际土壤样品进行实验验证。称取 1.00 g土壤样品,用20 mL超纯水混合均匀,超声提取40 min,离心后采用水系微孔滤膜过滤的前处理方式,土壤中高氯酸盐的加标回收率最稳定;在淋洗液浓度和流速都满足测定条件的前提下,为了缩短高氯酸盐的保留时间,避免复杂基质干扰,延长淋洗液发生器的使用寿命以及保护色谱柱,选择淋洗液浓度为40 mmol/L,流速为1.0 mL/min。在优化条件下,高氯酸盐的方法检出限为0.04 mg/kg。实际样品加标中高氯酸盐的相对标准偏差为1.9%~8.8%,加标回收率为91.0%~106%,结果表明离子色谱法测定土壤中高氯酸盐简单、灵敏、快速。     

离子色谱-串联质谱测定地表水中高氯酸盐

采用离子色谱-串联质谱测定地表水中高氯酸盐,在US EPA相应分析方法的基础上进行了优化,以阴离子交换柱为分析柱,氢氧化钾为淋洗液,经抑制电导检测后通过阀切换将检测液中大量弱保留的阴离子切到废液后再将强保留的高氯酸盐切入质谱,电喷雾负离子模式电离,选择离子反应监测(SIM)高氯酸盐。方法检出限达0.031μg/L,实际样品相对标准偏差为2.26%~4.45%,加标回收率为93.0%~98.0%。四川省内主要河流的高氯酸盐浓度在未检出~68.0μg/L之间,高氯酸盐污染不容忽视。     

Chloroacetic acids in European soils and vegetation

Trichloroacetic acid (TCA) and dichloroacetic acid (DCA) are possible minor atmospheric degradation products of perchloroethylene and trichloroethylene, respectively. These acids may be wet- or dry-deposited from the atmosphere to land surfaces and hence possibly affect plant growth. However, the existing database on TCA levels in soil is limited to a few studies carried out in the late 1980's and the early to mid-1990's and it was concluded that there is a need for further measurements of concentrations of TCA and DCA in soils. In this study soil samples from 10 locations in 5 European countries, as well as vegetation samples, and a limited number of rainwater and air samples were collected and analysed for DCA and TCA to determine the concentrations of these compounds. An isotope dilution method using GC-MS was used for the determination of these acids in the samples. The method was briefly validated and the performance characteristics are presented. The results of the analysis of the soil samples show that the DCA and TCA concentrations in soil from different sites in Europe are more or less comparable, with the exception of Germany, especially Freudenstadt, where significantly higher TCA concentrations (up to 12 microg kg(-1) dw) were found. The average DCA and TCA concentrations in soil in this study were 0.25 +/- 0.12 and 0.64 +/- 1.40 microg kg(-1) dw, respectively. Generally, the concentration in soils from forest areas are about twice those from open-land areas. The DCA and TCA concentrations in vegetation samples ranged from 2.1 to 73 microg kg(-1) dw for DCA and from 4.7 to 17 microg kg(-1) dw for TCA. Thus, the concentrations in vegetation samples are 10-20 times higher than the soil concentrations. DCA and TCA concentrations in wet deposition samples and air samples collected in The Netherlands were 0.14 and 0.15 microg l(-1) for wet deposition samples and <0.5 and 0.7 ng m(-3) for air samples respectively. For these samples taken in The Netherlands, the estimated values for soil and air concentrations calculated from the wet deposition concentrations are in agreement with the concentrations measured in this study.     

Adsorption and degradation of sulfosulfuron in soils

Adsorption of sulfosulfuron was studied in two soils (topsoil from Alfisol and Inceptisol). The adsorption of sulfosulfuron was greater in topsoil collected from Alfisol than in Inceptisol. The soil sorption coefficient K and the soil organic carbon sorption coefficient K _oc are the basic parameters used for describing the environmental fate of the herbicides. In topsoil the calculated K values from Alfisol was 4.43 and in topsoil from Inceptisol was 2.00. K _c values were 6.06 in topsoil from Alfisol and 3.33 in topsoil from Inceptisol. The K _oc values were 886.36 in topsoil from Alfisol and 770.26 in topsoil from Inceptisol. Field experimental plots with no previous history of sulfosulfuron were selected and studied the degradation of sulfosulfuron in the topsoil collected from Alfisol and Inceptisol. The half-life of sulfosulfuron in topsoil from Alfisol: T ₁− 3.97 days and T ₂− 4.54 days; topsoil from Inceptisol: T ₁ − 4.68 days and T ₂ − 5.52 days. The degradation of sulfosulfuron followed first-order kinetics. The persistence of sulfosulfuron was found relatively longer in the Inceptisol than in Alfisol. The combination of degradation data (t _1/2 – soil) and organic carbon based sorption (K _oc) data of herbicides have been used to assess the pesticide environmental impact in soils through Gustafson Ubiquity Score (GUS). The GUS values were found to be 0.69 in topsoil from Alfisol and 0.83 in Inceptisol.     

离子色谱法-抑制型电导检测城市污水中的高氯酸根

利用离子色谱法-抑制型电导检测了城市污水中的持久污染物高氯酸根,以IonPac AS20高容量强亲水阴离子交换柱分离,NaOH流动相等度淋洗,高氯酸根在12min内出峰。高氯酸根在0.01~50 mg/L内具有良好的线性,相关系数为0.9998,50μl进样时检出限可达到3μg/L。方法可用于多种城市污水中高氯酸根的监测,样品测定的标准相对偏差在0.60%~0.94%之间,加标回收率在97.3%~105.8%之间,具有较好的准确性和重现性。     

Methane fluxes in aerobic soils

Aerobic soils are an important sink for methane (CH₄), contributing up to 15% of global CH₄ destruction. However, the sink strength is significantly affected by land management, nitrogen (N) fertilizers and acidity. The rates of uptake from the atmosphere of both enhanced (10 ppmv) and ambient (2 ppmv) concentrations of CH₄ were measured in laboratory incubations of soil cores under controlled conditions taken from sites in the U.K. and Germany. The most rapid rates of uptake were measured in soil from deciduous woodland at pH 4 (measured in water). Extended (150 years) cultivation of land for arable crops reduced uptake rate by 85% compared to that in the same soil under an adjacent woodland. The long-term application of ammonium (NH₄)-based fertilizer, but not nitrate (NO₃)-based fertilizer, completely inhibited CH₄ uptake, but the application for the same period of farmyard manure (FYM) that contained more N than the fertilizer had no inhibitory effect. Where a combination of FYM and inorganic fertilizer was applied there was a reduction in methane uptake rate compared to plots receiving solely FYM.Autoclaving showed that the uptake of CH₄ was microbially mediated. The most likely causes of the inhibitory effects seen are (i) insufficient concentrations of CH₄ in situ to activate methane monooxygenase; (ii) the direct inhibition of CH₄ oxidation by NH _inf4 ^sup+ ions; (iii) the suppression of methanotrophs by NH₄-based fertilizers; (iv) the requirement of methanotrophs for a stable soil architecture which is incompatible with the disturbance caused by regular arable cultivation.     

Matrix-bound phosphine and phosphorus fractions in paddy soils

Phosphine (PH(3)) is a natural gaseous carrier of phosphorus (P) in its geochemical cycles, and it might be important to the P balance of natural ecosystems. Paddy fields are thought to be one of the main sources responsible for the production and emission of PH(3) in to the environment. The relationships between matrix-bound PH(3) (MBP) and different P fractions, as well as selected metals were investigated to explore the possible production of MBP and its link to P cycle in the paddy soils. MBP range from 20.8 (-1) to 502 ng kg(-1) with an average of 145 ng kg(-1). Concentrations at the milk stage are significantly higher than at the jointing stage. The total P range from 333 mg kg(-1) to 592 mg kg(-1). Average P fractions decrease in the order: Ca-P (69.9%) > Organic P (16.5%) > occluded P (6.50%) > Fe-P (5.93%) > dissolved P (0.80%) > exchangeable P (0.32%) > Al-P (0.02%). Different levels of nitrogen fertilizer have little effect on the contents of MBP, P fractions and metals. A significant positive correlation between MBP and Ca-P (p = 0.002), as well as between MBP and Ca (p = 0.008) could be observed, suggesting that Ca-P mainly affects the production of MBP in the paddy soils. It is suggested that soil MBP is strongly linked to Ca-P fertilizer use because soil spiked with P-fertilizer produced an additional 758 ± 142 ng of MBP per kg of soil, compared to only 81.7 ± 12.3 ng of MBP per kg of unspiked soil. No correlations are found between MBP and other P fractions, or between MBP and Al, Fe and Mn.