Multi-Residue Analysis of Herbicides in Soil with an UPLC-ESI-MS Method

A rapid and sensitive method was developed for the determination of 51 herbicides in soil by ultra-performance liquid chromatography-electrospray ionization-mass spectrometry (UPLC–ESI–MS). Using acetonitrile effectively extracted 22 kinds of triazine and other basic herbicides, and using 90:10 v/v acetonitrile-phosphate buffer (pH = 7.5) effectively extracted another 29 herbicides. The extract has not cleaned up further. Chromatographic separation was achieved within 10 min using gradient elution with acetonitrile–water as a mobile phase for 22 triazine and phenylurea herbicides, and with 5 mM ammonium acetate containing 0.1% formic acid aqueous solution–acetonitrile as a mobile phase for another 29 herbicides. The response was linear over two orders of magnitude with correlation coefficients (r²) higher than 0.99. The limits of quantification for the herbicides varied from 0.2 to 20 µg kg^?1. The intra- and inter-day precisions (relative standard deviation, RSD) were 2.2–9.3% and 5.7–17.1%, respectively. The average recovery varied from 61.6 to 112% with the RSD of 1.6–11.3%. Analyzing 51 soil samples from 17 counties formed the basis of this method. Three herbicide residues were found in four counties. Atrazine residue in soil for 17 counties was found; its content was 0.4–9.8 μg kg^?1. Nicosulfuron residue in soil for two counties was found, with a high up to 133 or 1317 μg kg^?1. Propazine (0.3 and 1.34 μg kg^?1), atratone (2.14 and 3.93 μg kg^?1), and cynanazine (0.34 μg kg^?1) in soils for some counties were also found. The validated method can ensure the rapid multi-class, multi-residue analysis at low μg kg^?1 level for 47 herbicides in soil. The developed method provides an effective analytical basis for controlling herbicide dosage, investigating their distribution and degradation, and evaluating their hazards on the environment and human health.     

Concentrations and Health Risk of Polycyclic Aromatic Hydrocarbons in Some Brands of Biscuits in the Nigerian Market

Concentrations of 16 priority polycyclic aromatic hydrocarbons (PAHs) were determined in 40 brands of biscuits in the Nigerian market. The analyses were performed by gas chromatography-flame ionisation detection (GC-FID) after Soxhlet extraction of the sample with hexane/dichloromethane and clean-up of the extract. The concentrations of Σ16 PAHs in these biscuit samples were in the range of 35.7–645.3 μg kg^?1, 75.9–490.7 μg kg^?1, 91.5–537 μg kg^?1, 18.4–522.2 μg kg^?1, 123.5–393.8 μg kg^?1, 167.2–880 μg kg^?1, 136.5–316 μg kg^?1, and 135.5–241.6 μg kg^?1 for shortcake, digestives, cookies, shortbread, wafers, crackers, Pringles, and cabin, respectively. The concentrations of Σ8 carcinogenic PAHs in the samples ranged from not detected (nd)–323.3 μg kg^?1, 15.7–138 μg kg^?1, 9.7–312.9 μg kg^?1, nd–331.7 μg kg^?1, nd–220.9 μg kg^?1, nd–53.3 μg kg^?1, 18.4–56.6 μg kg^?1, and 6.6–170.8 μg kg^?1 for shortcake, digestives, cookies, shortbread, wafers, crackers, Pringles, and cabin, respectively. The margin of exposure (MOE), based on PAH8 as an indicator for the occurrence and effects of PAHs in food, was less than 10,000, the serious health effects value, in 30% and 8% of the brands for the child and adult scenarios, respectively.     

Phytotoxicity of glyphosate soil residues re-mobilised by phosphate fertilisation

It has been repeatedly demonstrated that phosphate (P) and the herbicide glyphosate compete for adsorption sites in soils. Surprisingly, the potential consequences of these interactions for plants e.g. re-solubilisation of phytotoxic glyphosate residues in soils by application of P fertilisers or by root-induced mechanisms for P mobilization have not been investigated so far. In model experiments under greenhouse conditions, the potential for glyphosate re-mobilisation by P-fertiliser application was evaluated by bio-indication with soybean (Glycine max L.) cultivated on five contrasting soils with or without glyphosate application at 10?C35 days before sowing. Different levels of P-fertilisation (0, 20, 40, 80, 240 mg P kg^?1 soil) were supplied at the date of sowing. Visual symptoms of glyphosate toxicity, plant biomass, intracellular shikimate accumulation as physiological indicator for glyphosate toxicity and the plant nutritional status were determined. On glyphosate-treated soils, P application induced significant plant damage. Expression of damage symptoms declined in the order Arenosol > Acrisol ?? Ferralsol > Luvisol subsoil > Regosol. On the Arenosol, Ferralsol and Luvisol subsoil plant damage was associated with increased shikimate accumulation in the root tissue. On the Acrisol decline of germination and plant damage in absence of shikimate accumulation indicate toxicity of AMPA (aminomethylphosphonic acid) as the main metabolite of glyphosate in soils. On the Regosol, a growth-stimulating effect of glyphosate soil application (hormesis) was detected. The results suggest that re-mobilisation of glyphosate may represent an additional transfer pathway for glyphosate to non-target plants which is strongly influenced by soil characteristics such as P fixation potential, content of plant-available iron, pH, cation exchange capacity, sand content and soil organic matter.     

Exposure to aflatoxin B<Subscript>1</Subscript> in Thailand by consumption of brown and color rice

This study assessed the aflatoxin B₁ (AFB₁) intake of the Thai population through consumption of contaminated brown and color rice. A total of 240 rice samples from two harvesting periods were collected in June/July 2012 (period I) and in December 2012/January 2013 (period II) and analyzed for AFB₁ by HPLC with fluorescence detection (limit of detection (LOD)?=?0.093 ng/g). Exposure assessment was based on AFB₁ levels in rice and food intake data for rice according to Thai National Consumption. Frequency and levels of AFB₁ were higher in period I (59 %, <LOD?=?26.61 μg kg^?1) than in period II (10 %, <LOD?=?3.51 μg kg^?1). Only one sample exceeded the Thai standard limit for total aflatoxin of 20 μg kg^?1, but 12 out of 240 rice samples exceeded the European Union maximum level for AFB₁ of 2 μg kg^?1. The data showed that the quality and safety of Thai rice largely comply with the requirement for both exports and domestic consumption. According to the Thai National Consumption data, the estimated AFB₁ intake via rice consumption in period I and period II was 0.80 and 0.12 μg kg^?1 bw day^?1, respectively. The potential risk for cancer, based on the recommendation of the JECFA, was estimated to be 0.011 person/year/100,000 people at a mean consumption. Although the risk via consumption of Thai rice seems to be low, the maximum levels of AFB₁ in this staple food suggest that careful monitoring and surveillance of AFB₁ contamination in rice is essential to ensure the safety of rice.     

Hyperaccumulator Oilcake Manure as an Alternative for Chelate-Induced Phytoremediation of Heavy Metals Contaminated Alluvial Soils

The ability of hyperaccumulator oilcake manure as compared to chelates was investigated by growing Calendula officinalis L for phytoremediation of cadmium and lead contaminated alluvial soil. The combinatorial treatment T₆ [2.5 g kg^?1oilcake manure + 5 mmol kg^?1 EDDS] caused maximum cadmium accumulation in root, shoot and flower up to 5.46, 4.74 and 1.37 mg kg^?1and lead accumulation up to 16.11, 13.44 and 3.17 mg kg^?1, respectively at Naini dump site, Allahabad (S₃). The treatment showed maximum remediation efficiency for Cd (RR = 0.676%) and Pb (RR = 0.202%) at Mumfordganj contaminated site (S₂). However, the above parameters were also observed at par with the treatment T₅ [2.5 g kg^?1oilcake manure +2 g kg^?1 humic acid]. Applied EDDS altered chlorophyll–a, chlorophyll–b, and carotene contents of plants while application of oilcake manure enhanced their contents in plant by 3.73–8.65%, 5.81–17.65%, and 7.04–17.19%, respectively. The authors conclude that Calendula officinalis L has potential to be safely grown in moderately Cd and Pb-contaminated soils and application of hyperaccumulator oilcake manure boosts the photosynthetic pigments of the plant, leading to enhanced clean-up of the cadmium and lead-contaminated soils. Hence, the hyperaccumulator oilcake manure should be preferred over chelates for sustainable phytoremediation through soil-plant rhizospheric process.     

DDT and HCH (Organochlorine Pesticides) in Residential Soils and Health Assessment for Human Populations in Korba,India

Dichlorodiphenyltrichloroethane (DDT), hexachlorocyclohexane (HCH), and their isomers’ levels in residential soils were determined for the assessment of health risk in Korba, India. Observed concentrations of total HCH and total DDT in soils were more or less comparable with other parts of India and the world. ΣHCH and ΣDDT concentrations ranged between 0.9–20 μg kg^?1 and 2–315 μg kg^?1, respectively, which were lower than recommended soil quality guidelines indicating low ecotoxicological risk. Carcinogenic and non-carcinogenic impacts of HCH and DDT on human populations through soil ingestion were evaluated and presented. The incremental lifetime cancer risk (ILCR) for adults and children ranged between 7.8 × 10^?10–1.6 × 10^?7 and 4.1 × 10^?9–8.2 × 10^?7, respectively. Non-cancer health hazard quotient (HQ) ranged between 5.9 × 10^?7–1.8 × 10^?3 and 3.1 × 10^?6–9.4 × 10^?3, respectively, for adults and children. The estimated ILCR and HQ were within the safe acceptable limits of 10^?6–10^?4 and ≤1.0, respectively, indicating low risk to human populations from exposure to organochlorine pesticides (HCH and DDT) in the study area.     

Occurrence and risk assessment of organophosphorus pesticide residues in Chinese tea

Tea is the second widely consumed beverage next to water. Tea drinking is one of the important pathways for human exposure of organonphosphorus pesticide. Consequently, incidence of organonphosphorus pesticide residues and risk assessment should be clear. In this study, the level of organonphosphorus pesticide residues in 810 Chinese teas manufactured between 2010–2013 was investigated using gas chromatography coupled with tandem mass spectrometry and a flame photometric detector. Incidence of organonphosphorus pesticide residues occurred with a frequency of 29% and the average concentration of 93 μg kg^?1. The residue levels varied from tea types, sale spots, and production area. Chlorpyrifos, isocarbophos, and triazophos were the only three organonphosphorus pesticides with detectable residues, and the detectable rates were 13.0%, 13.6%, and 17.4%, respectively. The corresponding average daily intake of chlorpyrifos, isocarbophos, and triazophos by tea drinking was 0.000083 μg kg^?1 bw day^?1, 0.0036 μg kg^?1 bw day^?1, and 0.0022 μg kg^?1 bw day^?1. These results showed that the total hazard quotient of organonphosphorus pesticide pesticides from tea drinking was less than 0.02 and that the tea-drinking originated organonphosphorus pesticide exposure had a little adverse health effect for human being.     

Nitrogen cycling in forest soils across climate gradients in Eastern China

A ¹⁵N tracing study was carried out to investigate the potential gross nitrogen (N) dynamics in thirteen forest soils in Eastern China ranging from temperate to tropical zones (five coniferous forests, six deciduous broad-leaf forests, one temperate mixed forest, one evergreen broad-leaf forests ecosystems), and to identify the major controlling factors on N cycling in these forest ecosystems. The soil pH ranged from 4.3 to 7.9 and soil organic carbon (SOC) ranged from 6.6 g?kg^?1 to 83.0 g?kg^?1. The potential gross N transformation rates were quantified by ¹⁵N tracing studies where either the ammonium or nitrate pools were ¹⁵N labeled in parallel treatments. Gross mineralization rates ranged from 0.915 μg N g^?1 soil day^?1 to 2.718 μg N g^?1 soil day^?1 in the studied forest soils. The average contribution of labile organic-N (M _Nlab ) to total gross mineralization (M _Nrec +M _Nlab ) was 86% (58% to 99%), indicating that turnover of labile organic N plays a dominant role in the studied forest ecosystems. The gross mineralization rates in coniferous forest soils were significantly lower (ranging between 0.915 and 1.228 μg N g^?1 soil day^?1) compared to broad-leaf forest soils (ranging from 1.621 to 2.718 μg N g^?1 soil day^?1) (p?<?0.01). Thus, the dominant vegetation may play an important role in regulating soil N mineralization. Nitrate production (nitrification) occurred via two pathways, oxidation of NH ₄ ⁺ and organic N the forest soils. Correlations with soil pH indicated that this is a key factor controlling the oxidation of NH ₄ ⁺ and organic N in theses forest ecosystems. NH ₄ ⁺ oxidation decreased with a decline in pH while organic N oxidation increased. The climatic conditions (e.g. moisture status) at the various sites governed the NO ₃ ^? -N consumption processes (dissimilatory NO ₃ ^? reduction to NH ₄ ⁺ (DNRA) or immobilization of NO ₃ ^? ). Total NO ₃ ^? consumption and the proportion of total NO ₃ ^? consumption to total NO ₃ ^? production decreased with an increase in the drought index of ecosystems, showing that strong interactions appear to exist between climatic condition (e.g. the drought index), N mineralization and the rate of DNRA. Interactions between vegetation, climatic conditions govern internal N cycling in these forests soils.     

Heavy Metals Bioconcentration from Soil to Vegetables and Assessment of Health Risk Caused by Their Ingestion

The present study was undertaken to assess the non-carcinogenic human health risk of heavy metals through the ingestion of locally grown and commonly used vegetables viz. Raphanus sativus (root vegetable), Daucus carota (root vegetable), Benincasa hispida (fruit vegetable) and Brassica campestris leaves (leafy vegetable) in a semi-urbanized area of Haryana state, India. Heavy metal quantification of soil and vegetable samples was done using flame atomic absorption spectrophotometer. Lead, cadmium and nickel concentration in vegetable samples varied in range of 0.12–6.54 mg kg^?1, 0.02–0.67 mg kg^?1 and <0.05–0.41 mg kg^?1, respectively. Cadmium and lead concentration in some vegetable samples exceeded maximum permissible limit given by World Health Organization/Food and Agriculture Organization and Indian standards. Much higher concentrations of Pb (40–190.5 mg kg^?1), Cd (0.56–9.85 mg kg^-1) and Ni (3.21–45.87 mg kg^?1) were reported in corresponding vegetable fields’ soils. Correlation analysis revealed the formation of three primary clusters, i.e. Cu–Cd, Cd–Pb and Ni–Zn in vegetable fields’ soils further supported by cluster analysis and principal component analysis. Bioconcentration factor revealed that heavy metals’ uptake was more by leafy vegetable than root and fruit vegetables. Hazard index of all the vegetables was less than unity; thus, the ingestion of these vegetables is unlikely to pose health risks to the target population.     

<Emphasis Type="Italic">In vitro</Emphasis> sucrose concentration influences microtuber production and diosgenin content in white yam (<Emphasis Type="Italic">Dioscorea rotundata</Emphasis> Poir)

Dioscorea spp. is an important food crop in many countries and the source of the phytochemical diosgenin. Efficient microtuber production could provide source materials for farm-planting stock, for food markets, and for the production of high-diosgenin-producing cultivars. The first step in this study was optimizing the plant growth regulators for plantlet production, followed by a study of the effects of sucrose concentration on microtuber induction and diosgenin production. Significantly, more shoots (3.5) were produced at 4.65 μM (1 mg L^?1) kinetin (KIN), longer shoots (4.1 cm) were obtained at 2.46 μM (0.5 mg L^?1) indole-3-butyric acid (IBA), and root number (3.9) was significantly higher at 5.38 μM (1 mg L^?1) naphthalene acetic acid (NAA) than in other treatments. Increased sucrose concentrations in the optimized growth medium with 4.65 μM KIN and 5.38 μM NAA had significant effects on microtuber production (p < 0.01) and diosgenin content (p < 0.05). The most microtubers (6.2) were obtained with 100 g L^?1 sucrose, while those on 80 g L^?1 sucrose were the heaviest (0.7 g) and longest (7.4 mm). Microtubers formed in medium with 80 g L^?1 sucrose had significantly higher diosgenin content (3.64% [w/w]) than those in other sucrose treatments (< 2%) and was similar to that of field-grown parent tubers (3.79%). This result indicates an important role for sucrose in both microtuber growth and diosgenin production. Medium containing 4.65 μM KIN and 5.38 μM NAA is recommended for plantlet production, and medium containing 80 g L^?1 sucrose is recommended for microtuber and diosgenin production.     

Changes in bacterial CO2 fixation with depth in agricultural soils

Soils were incubated continuously in an atmosphere of ¹⁴CO₂ and the distribution of labeled C into soil organic carbon (¹⁴C-SOC) was determined at 0–1, 1–5, and 5–17 cm down the profile. Significant amounts of ¹⁴C-SOC were measured in paddy soils with a mean of 1,180.6?±?105.2 mg kg^–1 at 0–1 cm and 135.3?±?47.1 mg kg^?1 at 1–5 cm. This accounted for 5.9?±?0.7 % and 0.7?±?0.2 %, respectively, of the total soil organic carbon at these depths. In the upland soils, the mean ¹⁴C-SOC concentrations were 43 times (0–1 cm) and 11 times (1–5 cm) lower, respectively, than those in the paddy soils. The amounts of ¹⁴C incorporated into the microbial biomass (MBC) were also much lower in upland soils (5.0?±?3.6 % and 2.9?±?1.9 % at 0–1 and 1–5 cm, respectively) than in paddy soils (34.1?±?12.4 % and 10.2?±?2.1 % at 0–1 and 1–5 cm, respectively). Similarly, the amount of ¹⁴C incorporated into the dissolved organic carbon (DOC) was considerably higher in paddy soils (26.1?±?6.9 % and 6.9?±?1.3 % at 0–1 and 1–5 cm, respectively) than in upland soils (6.0?±?2.7 % and 4.3?±?2.2 %, respectively). The observation that the majority of the fixed ¹⁴C-SOC, RubisCO activity and cbbL gene abundance were concentrated at 0–1 cm depth and the fact that light is restricted to the top few millimeters of the soil profiles highlighted the importance of phototrophs in CO₂ fixation in surface soils. Phylogenetic analysis of the cbbL genes showed that the potential for CO₂ fixation was evident throughout the profile and distributed between both photoautotrophic and chemoautotrophic bacteria such as Rhodopseudomonas palustris, Bradyrhizobium japonicum, Rubrivivax gelatinosus and Ralstonia eutropha.     

Soil organic carbon dynamics 75 years after land-use change in perennial grassland and annual wheat agricultural systems

The dynamics of roots and soil organic carbon (SOC) in deeper soil layers are amongst the least well understood components of the global C cycle, but essential if soil C is to be managed effectively. This study utilized a unique set of land-use pairings of harvested tallgrass prairie grasslands (C₄) and annual wheat croplands (C₃) that were under continuous management for 75 years to investigate and compare the storage, turnover and allocation of SOC in the two systems to 1 m depth. Cropland soils contained 25 % less SOC than grassland soils (115  and 153 Mg C ha^?1, respectively) to 1 m depth, and had lower SOC contents in all particle size fractions (2000–250, 250–53, 53–2 and <2 μm), which nominally correspond to SOC pools with different stability. Soil bulk δ¹³C values also indicated the significant turnover of grassland-derived SOC up to 80 cm depth in cropland soils in all fractions, including deeper (>40 cm) layers and mineral-associated (<53 μm) SOC. Grassland soils had significantly more visible root biomass C than cropland soils (3.2 and 0.6 Mg ha^?1, respectively) and microbial biomass C (3.7 and 1.3 Mg ha^?1, respectively) up to 1 m depth. The outcomes of this study demonstrated that: (i) SOC pools that are perceived to be stable, i.e. subsoil and mineral-associated SOC, are affected by land-use change; and, (ii) managed perennial grasslands contained larger SOC stocks and exhibited much larger C allocations to root and microbial pools than annual croplands throughout the soil profile.     

Effect of Seawater–Sewage Cross-Transplants on Bacterial Metabolism and Diversity

Bioassays experiments were conducted to determine the metabolic and community composition response of bacteria to transplants between relatively pristine coastal seawater and sewage-impacted seawater. There were four treatments: (1) pristine seawater bacteria?+?pristine seawater (Pb?+?Pw), (2) sewage-impacted bacteria?+?sewage-impacted water (Sb?+?Sw), (3) pristine seawater bacteria?+?sewage-impacted water (Pb?+?Sw), and (4) sewage-impacted bacteria?+?pristine seawater (Sb?+?Pw). Sewage-derived DOC was more labile and readily utilized by bacteria, which favored the growth of high nucleic acid (HNA) bacteria, resulting in high bacterial production (BP, 113?±?4.92 to 130?±?15.8 μg C l^?1?day^?1) and low respiration rate (BR, <67?±?11.3 μg C l^?1?day^?1), as well as high bacterial growth efficiency (BGE, 0.68?±?0.09 to 0.71?±?0.05). In contrast, at the relatively pristine site, bacteria utilized natural marine-derived dissolved organic matter (DOM) at the expense of lowering their growth efficiency (BGE, <0.32?±?0.02) with low BP (<62?±?6.3 μg C l^?1?day^?1) and high BR 133?±?14.2 μg C l^?1?day^?1). Sewage DOM input appeared to alter the partitioning of carbon between respiration and production of bacteria, resulting in a shift toward higher BGE, which would not enhance oxygen consumption. Taxonomic classification based on 454 pyrosequencing reads of the 16S rRNA gene amplicons revealed that changes in bacterial community structure occurred when seawater bacteria were transferred to the eutrophic sewage-impacted water. Sewage DOM fueled the growth of Gammma-proteobacteria and Epsilson-proteobacteria and reduced the bacterial richness, but the changes in the community were not apparent when sewage-impacted bacteria were transferred to pristine seawater.     

Nitrous oxide and methane exchange in two small temperate forest catchments—effects of hydrological gradients and implications for global warming potentials of forest soils

The magnitude of greenhouse gas (GHG) flux rates may be important in wet and intermediate wet forest soils, but published estimates are scarce. We studied the surface exchange of methane (CH₄) and nitrous oxide (N₂O) from soil along toposequences in two temperate deciduous forest catchments: Strødam and Vestskoven. The soil water regime ranged from fully saturated to aerated within the catchments. At Strødam the largest mean flux rates of N₂O (15 μg N₂O-N m^?2 h^?1) were measured at volumetric soil water contents (SWC) between 40 and 60% and associated with low soil pH compared to smaller mean flux rates of 0-5 μg N₂O-N m^?2 h^?1 for drier (SWC < 40%) and wet conditions (SWC > 80%). At Vestskoven the same response of N₂O to soil water content was observed. Average CH₄ flux rates were highly variable along the toposequences (?17 to 536 μg CH₄-C m^?2 h^?1) but emissions were only observed above soil water content of 45%. Scaled flux rates of both GHGs to catchment level resulted in emission of 322 and 211 kg CO₂-equivalents ha^?1 year^?1 for Strødam and Vestskoven, respectively, with N₂O contributing the most at both sites. Although the wet and intermediate wet forest soils occupied less than half the catchment area at both sites, the global warming potential (GWP) derived from N₂O and CH₄ was more than doubled when accounting for these wet areas in the catchments. The results stress the importance of wet soils in assessments of forest soil global warming potentials, as even small proportions of wet soils contributes substantially to the emissions of N₂O and CH₄.     

NiO(s) (bunsenite) is not available to Alyssum species

To determine if the Ni-hyperaccumulator Alyssum corsicum can absorb Ni from the kinetically inert crystalline mineral NiO(s) (bunsenite). A. corsicum and A. montanum plants were grown for 30 days in a serpentine Hoagland solution. NiO was provided at 0 or 0.1 g L^?1 (1.34 mmol L^?1) as reagent grade NiO particles <1 μm diameter, continuously mixed by aeration. A. corsicum and A. montanum shoots contained 19.4 and 5.2 mg Ni kg^?1 DW with NiO, and 3.0 and 1.1 mg Ni kg^?1 DW shoots, respectively in the control treatment. A. corsicum normally absorbs over 12,000 mg Ni kg^?1 shoots when supplied 300 μM soluble Ni. Roots were coated with the NiO particles and contained 3–5% Ni at harvest. Despite the small Ni accumulation in the NiO treatment above control, A. corsicum is not capable of dissolving and hyperaccumulating Ni from NiO.     

A Study on Cadmium Phytoremediation Potential of Indian Mustard,Brassica juncea

The objective of this study was to investigate Cd phytoremediation ability of Indian mustard, Brassica juncea. The study was conducted with 25, 50, 100, 200 and 400 mg Kg^?1 CdCl₂ in laboratory for 21 days and Cd concentrations in the root, shoot and leaf tissues were estimated by atomic absorption spectroscopy. The plant showed high Cd tolerance of up to 400 mg Kg^?1 but there was a general trend of decline in the root and shoot length, tissue biomass, leaf chlorophyll and carotenoid contents. The tolerance index (TI) of plants were calculated taking both root and shoot lengths as variables. The maximum tolerance (TI _shoot = 87.4 % and TI _root = 89.6 %) to Cd toxicity was observed at 25 mg Kg^?1, which progressively decreased with increase in dose. The highest shoot (10791 μg g^?1 dry wt) and root (9602 μg g^?1 dry wt) Cd accumulation was achieved at 200 mg kg^?1 Cd treatment and the maximum leaf Cd accumulation was 10071.6 μg g^?1 dry wt achieved at 100 mg Kg^?1 Cd, after 21 days of treatment. The enrichment coefficient and root to shoot translocation factor were calculated, which, pointed towards the suitability of Indian mustard for removing Cd from soil.     

Toxicity of an Annonin-Based Commercial Bioinsecticide Against Three Primary Pest Species of Stored Products

The effects of a bioinsecticide formulation based on extract of Annona squamosa L. (Annonaceae) containing 10,000 mg L^?1 of acetogenin annonin as the main active ingredient were investigated against three primary pest species of stored grains in Brazil [maize weevil Sitophilus zeamais Motschulsky (Coleoptera: Curculionidae), Mexican bean weevil Zabrotes subfasciatus (Boheman) (Coleoptera: Chrysomelidae: Bruchinae), and cowpea weevil Callosobruchus maculatus (Fabricius) (Coleoptera: Chrysomelidae: Bruchinae)] by means of residual contact bioassays. In a concentration-dependent manner, the annonin-based commercial bioinsecticide caused significant adult mortality of C. maculatus (LC₅₀ = 6890 μL kg^?1), S. zeamais (LC₅₀ = 2781 μL kg^?1), and Z. subfasciatus (LC₅₀ = 2120 μL kg^?1) after 120 h of residual contact exposure. In addition to acute toxicity, the tested bioinsecticide also promoted a significant reduction of the number of eggs laid by females of C. maculatus (EC₅₀ = 5949.7 μL kg^?1) and Z. subfasciatus (EC₅₀ = 552.7 μL kg^?1). Moreover, the bioinsecticide significantly reduced the number of emerged insects (F₁ generation) of C. maculatus (EC₅₀ = 2763.0 μL kg^?1), S. zeamais (EC₅₀ = 1380.8 μL kg^?1), and Z. subfasciatus (EC₅₀ = 561.5 μL kg^?1). The bioinsecticide also reduced the percentage of damaged grains for the three pest species studied, and its grain-protectant properties are comparable to or superior in efficacy in relation to a diatomaceous earth-based insecticide (Insecto® at 1000 mg kg^?1) used as a positive control. Thus, this standardized formulation has promising bioactivity against stored insect species and can be a useful component for IPM of stored grains in Brazil and elsewhere.     

Enhanced phytoremediation of cadmium and/or benzo(a)pyrene contaminated soil by hyperaccumlator Solanum nigrum L.

The role of same amendment on phytoremediating different level contaminated soils is seldom known. Soil pot culture experiment was used to compare the strengthening roles of cysteine (CY), EDTA, salicylic acid (Sa), and Tween 80 (TW) on hyperaccumulator Solanum nigrum L. phytoremediating higher level of single cadmium (Cd) or Benzo(a)pyrene (BAP) and their co-contaminated soils. Results showed that the Cd capacities (ug pot^?1) in shoots of S. nigrum in the combined treatment T_{0.1EDTA+0.9CY} were the highest for the 5 and 15 mg kg^?1 Cd contaminated soils. When S. nigrum remediating co-contaminated soils with higher levels of Cd and BAP, that is, 5 mg kg^?1 Cd + 1 mg kg^?1 BAP and 15 mg kg^?1 Cd + 2 mg kg^?1 BAP, the treatment T_{0.9CY+0.9Sa+0.3TW} showed the best enhancing remediation role. This results were different with co-contaminated soil with 0.771 mg kg^?1 Cd + 0.024 mg kg^?1 BAP. These results may tell us that the combine used of CY, SA, and TW were more useful for the contaminated soils with higher level of Cd and/or BAP. In the combined treatments of Sa+TW, CY was better than EDTA.     

A Counter-Current Acid Leaching Process for the Remediation of Contaminated Soils from a Small-Arms Shooting Range

The objective of this research was to use a counter-current leaching process (CCLP) with leachate treatment to develop a remediation process for contaminated soils at a small-arms shooting range (SASR). The soil contaminant concentrations were 245 mg Cu kg^?1, 3,368 mg Pb kg^?1, 73 mg Sb kg^?1, and 177 mg Zn kg^?1. The CCLP includes three acid leaching steps (1M H₂SO₄ + 4M NaCl, t = 1 h, T = 20°C, soil suspension = 100 g L^?1), followed by one water rinsing step (1 h). Seven counter-current remediation cycles were completed, and the average resulting metal removals were 93.2 ± 3.5% of Cu, 91.5 ± 5.7% of Pb, 82.2 ± 10.9% of Sb, and 30.0 ± 11.4% of Zn. The metal leaching performances decreased with the number of completed cycles. Soil treated with the CCLP with leachate treatment process met the USEPA threshold criteria of 5 mg Pb L^?1 in the TCLP leachate. The CCLP allows a decrease of the water use by 32.9 m³ t^?1 and the chemicals’ consumption by approximately 2,650 kg H₂SO₄, 6,014 kg NaCl, and 1,150 kg NaOH per ton of treated soil, in comparison to standard leaching processes. This corresponds to 78%, 69%, 83%, and 67% of reduction, respectively.     

Counter-Current Metal Leaching and Precipitation for Soil Remediation

Chemical acid leaching is an effective technique for extracting toxic metals from the finest fractions of polluted soils. Nevertheless, the use of large quantities of reagents and process water results in prohibitive operating costs. The purpose of this study was to evaluate the technical and economic advantages of recirculating water in a counter-current leaching process (CCLP). Five 1-h sulfuric acid extraction steps (at pH = 1.5) followed by three 5-min water-washing steps were applied to the fine particle fraction (<0.125 mm) of an industrial soil polluted by Cd (13.2 mg·kg^?1), Cu (3 100 mg·kg^?1), Mn (685 mg kg^?1), Pb (550 mg·kg^?1), and Zn (2 840 mg·kg^?1). The leaching experiments were carried out at ambient temperature using a 10% soil suspension and in 1-L working volume stirred tank reactors. This paper presents results of conventional and counter-current leaching process (CCLP) tests and shows that the CCLP yields removal results for Cu (85%), Zn (86%), Mn (75%), and Cd (90%) that are similar to those obtained using the conventional leaching process. Moreover, the CCLP uses half of the quantity of acid and one-eighth of the amount of water that the conventional process uses. Metal precipitation with NaOH and Ca(OH)₂ was applied to treat the acidic leachates, and good metal removal yields were achieved with both reagents. However, the large consumption of chemicals implies high operating costs. In addition, the precipitation causes considerable sludge production, particularly when using Ca(OH)₂. Overall, the CCLP coupled to metal precipitation using NaOH and water recycling appears to be the most attractive option for the removal of toxic metals from this industrial soil.