Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.     

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid–liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25–25 µg L^?1 of 1.25–20 µg L^?1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.     

Removal mechanisms and kinetics of trace tetracycline by two types of activated sludge treating freshwater sewage and saline sewage

Understanding the removal mechanisms and kinetics of trace tetracycline by activated sludge is critical to both evaluation of tetracycline elimination in sewage treatment plants and risk assessment/management of tetracycline released to soil environment due to the application of biosolids as fertilizer. Adsorption is found to be the primary removal mechanism while biodegradation, volatilization, and hydrolysis can be ignored in this study. Adsorption kinetics was well described by pseudo-second-order model. Faster adsorption rate (k ₂?=?2.04?×?10^?2?g?min^?1?μg^?1) and greater adsorption capacity (q _e?=?38.8 μg?g^?1) were found in activated sludge treating freshwater sewage. Different adsorption rate and adsorption capacity resulted from chemical properties of sewage matrix rather than activated sludge surface characteristics. The decrease of tetracycline adsorption in saline sewage was mainly due to Mg²⁺ which significantly reduced adsorption distribution coefficient (K _d) from 12,990?±?260 to 4,690?±?180 L?kg^?1. Species-specific adsorption distribution coefficients followed the order of $ K_{\mathrm{d}}^{{ + 00}} \gg K_{\mathrm{d}}^{{ + - 0}} > K_{\mathrm{d}}^{{ + - - }} $ . Contribution of zwitterionic tetracycline to the overall adsorption was >90 % in the actual pH range in aeration tank. Adsorption of tetracycline in a wide range of temperature (10 to 35 °C) followed the Freundlich adsorption isotherm well.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg^?1) and DEHP (100 mg kg^?1) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1–0.45 μm to 500–2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

The effect of consumption of pork enriched by organic selenium on selenium status and lipid profile in blood serum of consumers

Abstract

The aim of the research was to evaluate the effect of consumption of selenium-enriched pork on selected health indicators of probands. The intake of feed mixture with increased organic selenium at the dose of 0.3?mg.kg^?1 probably increases selenium concentration in MSM (musculus semimembranosus). In the pork enriched with organic selenium, the concentration was higher by 1.045?±?0.10?mg.kg^?1 compared with the control group 0.701?±?0.05?mg.kg^?1 at significance P?<?0.001. Sixteen participants in the experiment were represented by 8 men at the average age of 41.5?±?11.9?years and 8 women at the average age of 41.4?±?7.9?years. All the probands consumed meat enriched with selenium three times a week during one month. By consumption of the enriched pork, there was an increase of the selenium concentration in blood serum of probands traced with selenium increase from 73.19?±?15.68?μg.L^?1 to 73.73?±?15.13?μg.L^?1 (P?>?0.05). From the results we can see that consumption of enriched pork with selenium was significantly manifested in lowering of total cholesterol levels, which was associated with LDL cholesterol lowering (P?<?0.05). Differences among the HDL cholesterol and triglycerides samples were not significant.     

Long-term study of palladium in road tunnel dust and sewage sludge ash

The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 μg Pd kg⁻¹ were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 μg Pd kg⁻¹ were found in the years 1986-1997. In both matrices correlations of Pd content to Pd demand of industry are discussed.     

Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna)

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL^?1 for OCs and OPs and 0.05–2.5 μg mL^?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg^?1, and the LOQs were determined as 0.01-0.049 mg kg^?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.     

A simple HPLC method for determination of permethrin residues in wine

An isocratic High Performance Liquid Chromatographic (HPLC) method was optimized for 3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate (permethrin) residues identification and quantification in wine matrix. Analytical reverse phase (RP) C-18 column was used (25 cm × 4 mm i.d., 5 μ m) with mobile phase consisting of acetonitrile and water in ratio 70 %/30 % (v v^?1), flow-rate 2.0 mL min^?1, UV-detection at 215 nm and controlled oven temperature at 25°C. The peaks of isomers were identified with the retention times as compared to standard cis-/trans- mixture and confirmed with characteristic spectra using photodiode array detector. Under these conditions, permethrin isomers were well separated with resolution 2.8 and no interference with the naturally present wine compounds was observed. The method was validated for linearity, precision, accuracy, limit of detection (LOD) and limit of quantification (LOQ). Linear regression analysis data proved a good linear relationship (correlation coefficients, r², for cis- and trans-isomer are: 0.9995 and 0.9997, respectively) between response of the detector and concentration of permethrin isomers over a wide concentration range for both isomers (0.55 mg L^?1 ?4.40 mg L^?1). Experimental data showed mean recoveries between 93.95% and 96.58% with RSD values in range: 0.89% ?3.69%. The effect of ethanol content in the solvent on permethrin isomers peak areas was also studied and 60% v v^?1 ethanol was found to be optimal for sample preparation. The method was successfully tested on 20 commercial wine samples from the market in which no permethrin was detected. Thus, it was proved that it is suitable for routine permethrin residues analysis. The proposed method is suitable for routine analysis because of the simple sample preparation, acceptable run-time, low cost and its applicability with conventional instruments.     

Determination of glyphosate residue in maize and rice using a fast and easy method involving liquid chromatography–mass spectrometry (LC/MS/MS)

A fast and easy method was developed for the determination of glyphosate in maize and rice by using liquid chromatography triple quadrupole mass spectrometry with a Dionex Ion Pack column and phosphate buffer mobile phase. Samples were extracted with an acidified methanol solution. An isotope-labeled internal standard was added to the sample before extraction to ensure accurate tracking and quantification. The method’s performance was evaluated through a series of assessments to determine the accuracy, precision, linearity, matrix effect, limit of detection (LOD), and limit of quantification (LOQ). The mean recoveries for both matrices were within 70–105% at three fortification levels, including the LOQ. The precision for replicates was <20% (RSD%) for both matrices. Good linearity (R²=0.9982) was obtained over the concentration range of 0.01–1.5?mg kg^?1. The LOD was determined to be 0.002?mg kg^?1 for rice and 0.004?mg kg^?1 for maize. The LOQ was 0.01?mg kg^?1 for both maize and rice. Due to its versatility, the proposed method could be considered useful for the determination of glyphosate in cereals in routine analysis.     

The effects of different sewage sludge amendment rates on the heavy metal bioaccumulation,growth and biomass of cucumbers (Cucumis sativus L.)

When sewage sludge is incorrectly applied, it may adversely impact agro-system productivity. Thus, this study addresses the reaction of Cucumis sativus L. (cucumber) to different amendment rates (0, 10, 20, 30, 40 and 50 g kg^?1) of sewage sludge in a greenhouse pot experiment, in which the plant growth, heavy metal uptake and biomass were evaluated. A randomized complete block design with six treatments and six replications was used as the experimental design. The soil electrical conductivity, organic matter and Cr, Fe, Zn and Ni concentrations increased, but the soil pH decreased in response to the sewage sludge applications. As approved by the Council of European Communities, all of the heavy metal concentrations in the sewage sludge were less than the permitted limit for applying sewage sludge to land. Generally, applications of sewage sludge of up to 40 g kg^?1 resulted in a considerable increase in all of the morphometric parameters and biomass of cucumbers in contrast to plants grown on the control soil. Nevertheless, the cucumber shoot height; root length; number of leaves, internodes and fruits; leaf area; absolute growth rate and biomass decreased in response to 50 g kg^?1 of sewage sludge. All of the heavy metal concentrations (except the Cu, Zn and Ni in the roots, Mn in the fruits and Pb in the stems) in different cucumber tissues increased with increasing sewage sludge application rates. However, all of the heavy metal concentrations (except the Cr and Fe in the roots, Fe in the leaves and Cu in the fruits) were within the normal range and did not reach phytotoxic levels. A characteristic of these cucumbers was that all of the heavy metals had a bioaccumulation factor <1.0. All of the heavy metals (except Cd, Cu and Zn) had translocation factors that were <1.0. As a result, the sewage sludge used in this study could be considered for use as a fertilizer in cucumber production systems in Saudi Arabia and can also serve as a substitute method of sewage sludge disposal.

The effects of different sewage sludge amendment rates on the heavy metal bioaccumulation, growth and biomass of cucumbers

     

Organochlorine pesticides and polychlorinated biphenyls in soils surrounding the Tanggu Chemical Industrial District of Tianjin, China

The spatial distribution of persistent organic pollutants (POPs) was examined in soils surrounding the Tanggu Chemical Industrial District in Tianjin, China. The concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzenes (HCBs), and polychlorinated biphenyls (PCBs) were determined in 70 surface soils using accelerated solvent extraction and gas chromatography with electron capture detection. The results showed that the ranges of ∑HCH, ∑DDT, ΣHCB, and ∑PCB concentrations in soils were 2.1–12,549 μg?kg^?1 (average, 965 μg?kg^?1), n.d.–2,033 μg?kg^?1 (average, 88.4 μg?kg^?1), n.d.–1,924 μg?kg^?1 (average, 349 μg?kg^?1), and n.d.–373 μg?kg^?1 (average, 46.2 μg?kg^?1), respectively. Of these, HCHs were the dominant POPs, accounting for 75 % of the total organochlorine pesticide (OCP) residues. Overall, the spatial distribution of OCP concentrations showed a decreasing trend from the center of the Tanggu District to the surrounding areas. Two major pollution sources were Tianjin Dagu Chemical Co., Ltd. in the district center and the Tianjin Chemical Plant in Hangu District. In contrast, PCB concentrations were relatively high in the Haihe estuary to the east and low to the west of the study area. Component analysis of OCPs in these soils showed that they mainly came from industrial point sources. Compared with soils in other regions, soil DDT pollution was at a medium level in the Tanggu Chemical Industrial District, but associated HCH, HCB, and PCB pollution was relatively heavy. By multivariate statistical analyses, Tianjin Dagu Chemical Co., Ltd. was recognized as the main source of POPs, and soil properties were clarified to play an important role on the distribution and composition of POPs, especially the organic carbon content.     

Adsorption/Desorption of Copper by a Sandy Soil Amended with Various Rates of Manure,Sewage Sludge,and Incinerated Sewage Sludge

Organic amendments are sometimes applied to agricultural soils to improve the physical, chemical, and microbiological properties of the soils. The organic fractions in these soil amendments also influence metal reaction, particularly the adsorption and desorption of metals, which, in turn, determine the bioavailability of the metals and hence their phytotoxicities. In this study, a Quincy fine sandy (mixed, mesic, Xeric Torripsamments) soil was treated with 0 to 160 g kg^?1 rates of either manure, sewage sludge (SS), or incinerated sewage sludge (ISS) and equilibrated in a greenhouse at near field capacity moisture content for 100 days. Following the incubation period, the soil was dried and adsorption of copper (Cu) was evaluated in a batch equilibration study at either 0, 100, 200, or 400 mg L^?1 Cu concentrations in a 0.01M CaCl₂ solution. The desorption of adsorbed Cu was evaluated by three successive elutions in 0.01M CaCl₂. Copper adsorption increased with an increase in manure rates. At the highest rate of manure addition (160 g kg^?1 soil), Cu adsorption was two-fold greater than that by the unamended soil at all rates of Cu additions. With increasing rates of Cu additions, the adsorption of Cu decreased from 99.4 to 77.6% of Cu applied to the 160 g kg^?1 manure amended soil. The desorption of Cu decreased with an increase in rate of manure amendment. Effects of sewage sludge amendments on Cu adsorption were somewhat similar to those as described for manure additions. Likewise, the desorption of Cu was the least at the high rate of SS addition (160 g kg^?1), although at the lower rates there was not a clear indication of the rate effects. In contrast to the above two amendments, the ISS amendment had the least effect on Cu adsorption. At the highest rate of ISS amendment, the Cu adsorption was roughly 50% of that at the similar rate of either manure or SS amendments, across all Cu rates.     

Occurrence and environmental implications of pharmaceuticals in Chinese municipal sewage sludge

The presence of pharmaceuticals in aquatic environment has become a topic of concern because of their potential adverse effects on human health and wildlife species. A total of 45 dewatered sewage sludge samples were collected throughout China and analyzed for 30 commonly consumed pharmaceutical residues. Ofloxacin was found to be the dominant contaminant with concentrations up to 24 760 μg kg⁻¹, followed by oxytetracycline (5280 μg kg⁻¹), norfloxacin (5280 μg kg⁻¹) and ketoprofen (4458 μg kg⁻¹). The concentration of pharmaceutical residues varied greatly depending on the operation conditions of wastewater treatment plants and sampling locations. Poor agreement was found between the predicted (calculation based on the annual consumption and coefficient of sludge water partition) and detected concentrations of the pharmaceuticals indicating that the occurrence of pharmaceutical residues was affected by various factors such as loading rates, sewage properties and the chemical properties such as the contribution from polar groups. National wide fate and ecotoxicity study is required for the development of control strategies.     

Quantification of ionophores in aged poultry litter using liquid chromatography tandem mass spectrometry

Veterinary anticoccidials, biochemically known as ionophores, are widely used in poultry feed at therapeutic levels to treat Coccidiosis and at sub-therapeutic levels for growth- promotion. Commonly used ionophores in the US poultry industry are monensin, salinomycin, lasalocid and narasin. There is an increasing concern regarding the persistence of these anticoccidials in the environment. However, little attention has been directed to methods development for quantitatively measuring ionophores in complex environmental matrices such as poultry litters that are land applied. Here, we describe a rapid and sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS)-based method developed for simultaneous quantification of monensin, lasalocid, salinomycin, and narasin in aged poultry litter samples. Results show significant level of monensin (97.8 ± 3.2 μg kg^?1), lasalocid (19.2 ± 6.6 μg kg^?1), salinomycin (70 ± 2.7 μg kg^?1) and narasin (57.3 ± 2.6 μg kg^?1) in poultry litter stored for over three years at < 5°C. Our findings indicate that even after several years of unmanaged storage of poultry litter, ionophores may continue to persist in this matrix, raising the possibility of prolonged release into the environment.     

Antibiotic uptake by plants from manure-amended soils

Antibiotics are extensively given to livestock to promote growth and reduce diseases. Therefore, animal manure often contains antibiotics. Once manure is applied to agricultural land to improve soil productivity, crops would be exposed to antibiotics which may persist in soils from a few to several hundred days. The objective of this study was to evaluate the uptake of gentamicin and streptomycin by carrot (Daucus carota), lettuce (Lactuca sativa) and radish (Rhaphanus sativus) from manure-amended soil. The treatments were 0, 0.5 and 1 mg of antibiotic kg^?1 of soil. Two pot experiments were carried out in the greenhouse. The first was conducted on the three crops and the second exclusively on radish. In radish, the increase in the concentrations of gentamicin was significant between the 0 and both of 0.5 and 1.0 mg kg^?1 treatments, but not significant between the 0.5 and 1.0 mg kg^?1. The average values were 35.5, 60.0 and 57.4 μg kg^?1 for the 0, 0.5 and 1 mg kg^?1 rates, respectively. However, the increase in streptomycin concentration in radish was not significant between the three treatments, and the average values were, 12.1, 15.2 and 17.4 μg kg^?1 for the 0, 0.5 and 1 mg kg^?1 rates, respectively. In carrot roots and lettuce leaves no significant increase in the concentrations of gentamicin or streptomycin was observed between the treatments. The three crops absorbed relatively higher amounts of gentamicin (small molecule) than streptomycin (large molecule). Generally the levels of antibiotics in plant tissue increased with increasing the antibiotic concentration in the manure (1 mg kg^?1 > 0.5 mg kg^?1).     

Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947 ng kg⁻¹ dw (0.02-49.9 ng WHO-TEQ kg⁻¹ dw) for 17 PCDD/Fs, 17.5-66 761 μg kg⁻¹ dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29 604 μg kg⁻¹ dw for hexabromocyclododecanes (HBCDs) (α-, β-, and γ-diastereomers), and 4.01-618 μg kg⁻¹ dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, β-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.     

Detection of free microcystins in the liver and muscle of freshwater fish by liquid chromatography-tandem mass spectrometry

MC analysis of biological tissue is considered to be very difficult due to the lack of validated methods. This is the primary limiting factor for monitoring potential risks in both the flesh of aquatic organisms and the aquatic ecosystem. In this study, an effective method to determine free MCs (MC-LR and MC-RR) in the muscle and liver tissues of freshwater cultured fish was developed using solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC/MS-MS). The extraction solvent, time of extraction, eluent and purification of the extract were optimized. Various SPE cartridges were also investigated. In this optimized analytical procedure, an 85% methanol/water solution (v/v) was selected as the extraction solvent, after which the extracts were purified by removing fats and proteins; a HLB cartridge was chosen for MCs enrichment; and 90% methanol containing 0.02% formic acid/water solution (v/v) was used as the eluent. Under the optimized pretreatment conditions and instrument parameters, good recoveries of MC-LR and MC-RR were obtained at three concentrations (0.5, 1.0 and 2.0 µg g^?1 dry weight (DW)), with values ranging from 92.5 to 98.3% and 92.1 to 98.6%, respectively. The method detection limit (MDL) for muscle samples was 0.5 µg kg^?1 and 0.4 µg kg^?1 (DW) for MC-LR and MC-RR, respectively. The MDL for the liver samples was 0.8 µg kg^?1 (DW) for both MC-LR and MC-RR. The developed procedure was successfully applied to analyze MCs in the muscle and liver of fish samples collected from a Chinese freshwater aquaculture pond during bloom seasons. The MC-LR concentrations ranged from below the MDL to 4.17 µg kg^?1 and the MC-RR concentrations ranged from below the MDL to 2.64 µg kg^?1.     

Environmental and Potential Health Effects of Growing Leafy Vegetables on Soil Irrigated Using Sewage Sludge and Effluent: A Case of Zn and Cu

Abstract

The use of sewage sludge and effluent as a source of nutrients and water for crop production is increasing worldwide. A study was conducted in 2001 at Pension farm (near Harare) to determine the effect of long term (>30 yrs) application of sewage sludge and effluent on Zn and Cu accumulation in top soil, uptake of these metals by lettuce (Lactuca sativa L.) and mustard rape (Brassica juncea L.), and dry matter yield. Application of sewage sludge/effluent significantly (p < 0.001) increased total Zn (13.7–1563.9 mg kg^?1) and Cu (2.5–133.3 mg kg^?1) in the top soil (0–20 cm depth) compared to the control. Sewage sludge/effluent addition significantly (p < 0.001) increased Zn uptake by both test crops, while Cu uptake was significant in the first crop of lettuce and the second crop of mustard rape. Based on the dietary patterns of poor urban households in Zimbabwe, the maximum possible intake of Cu will only constitute 40% the Maximum Daily Intake (MDI). The toxicological implications for Zn will however be more severe, exceeding the MDI by 77% through exposure by lettuce consumption and by 251% consumption of mustard rape. It was concluded that long-term addition of sewage sludge/effluent to soil at Pension farm had increased the concentration of Zn and Cu in top soil to levels that pose environmental concern. The consumption of leafy vegetables produced on these soils pose a health risk to poor communities that reside around the study site, especially children, through possible Zn toxicity.     

Selenium,total mercury and methylmercury in sardine: Study of molar ratio and protective effect on the diet

The purpose of this work was to evaluate the risk-benefit associated with canned sardine consumption, considering the selenium, the mercury and the methylmercury contents and the Se:Hg molar ratio and the Se-health benefit value (HBV) index. In this study, 63 canned sardine samples were purchased worldwide and for the determination of selenium and mercury species, the inductively coupled plasma optical emission spectrometry and thermal decomposition and amalgamation atomic absorption spectrometry were employed. The mean results obtained for the Brazilian samples varied between 12.6 and 65.5?μg kg^?1 for Hg; <3.7 and 45.4?μg kg^?1 for methylmercury; 310 and 1370?μg kg^?1 for Se. The MeHg/Hg ratio showed that the most toxic forms of Hg (MeHg) is predominant in 52 and 39% of the Brazilian samples conserved in tomato sauce and in oil, respectively. Nevertheless, the Se-HBV index and the Hg:Se and Se:Hg molar ratios indicated that the selenium content in canned sardine samples is enough to provide a protective effect on the Hg species.     

Method validation for control determination of mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry

A method for the determination of total mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) has been validated following international foodstuff protocols in order to fulfill the Brazilian National Residue Control Plan. The experimental parameters have been previously studied and optimized according to specific legislation on validation and inorganic contaminants in foodstuff. Linearity, sensitivity, specificity, detection and quantification limits, precision (repeatability and within-laboratory reproducibility), robustness as well as accuracy of the method have been evaluated. Linearity of response was satisfactory for the two range concentrations available on the TDA AAS equipment, between approximately 25.0 and 200.0 μg kg^?1 (square regression) and 250.0 and 2000.0 μg kg^?1 (linear regression) of mercury. The residues for both ranges were homoscedastic and independent, with normal distribution. Correlation coefficients obtained for these ranges were higher than 0.995. Limits of quantification (LOQ) and of detection of the method (LDM), based on signal standard deviation (SD) for a low-in-mercury sample, were 3.0 and 1.0 μg kg^?1, respectively. Repeatability of the method was better than 4%. Within-laboratory reproducibility achieved a relative SD better than 6%. Robustness of the current method was evaluated and pointed sample mass as a significant factor. Accuracy (assessed as the analyte recovery) was calculated on basis of the repeatability, and ranged from 89% to 99%. The obtained results showed the suitability of the present method for direct mercury measurement in fresh fish and shrimp samples and the importance of monitoring the analysis conditions for food control purposes. Additionally, the competence of this method was recognized by accreditation under the standard ISO/IEC 17025.