Heavy metal contamination and risk assessment in water,paddy soil,and rice around an electroplating plant

Purpose  

The objective of this paper is to assess the impact of long-term electroplating industrial activities on heavy metal contamination in agricultural soils and potential health risks for local residents.     

Photodegradation of multiclass fungicides in the aquatic environment and determination by liquid chromatography-tandem mass spectrometry

Environmental Science and Pollution Research - The photodegradation behaviour for nine widespread fungicides (benalaxyl, cyprodinil, dimethomorph, fenhexamide, iprovalicarb, kresoxim-methyl,...     

Detection of free and covalently bound microcystins in animal tissues by liquid chromatography-tandem mass spectrometry

Microcystins are cyanobacterial hepatotoxins capable of accumulation into animal tissues. The toxins act by inhibiting specific protein phosphatases and both non-covalent and covalent interactions occur. The 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) method determines the total, i.e. the sum of free and protein-bound microcystin in tissues. The aim of the method development in this paper was to tackle the problems with the MMPB methodology: the rather laborious workflow and the loss of material during different steps of the method. In the optimised workflow the oxidation recovery was of acceptable level (29-40%), the extraction efficiency good (62-97%), but the signal suppression effect from the matrix remained severe in our system (16-37% signal left). The extraction efficiency for the determination of the free, extractable microcystins, was found to be good, 52-100%, depending on the sample and the toxin variant and concentration.     

Continental bottled water assessment by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry (SBSE-GC-MS/MS)

This study was aimed to determine the presence of 69 organic contaminants in 77 representative bottled waters collected from 27 countries all over the world. All water samples were contained in polyethylene terephthalate bottles. Target compounds were (1) environmental contaminants (including 13 polycyclic aromatic hydrocarbons (PAHs), 31 pesticides including organochlorine (OCPs), organophosphorus, and pyrethroids; 7 polychlorinated biphenyls (PCBs); and 7 triazines) and (2) plasticizers (including 6 phthalates and 5 other compounds). Samples were analyzed by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry. PAHs, OCPs, PCBs, and triazines, which are indicators of groundwater pollution, were not detected in most of the samples, except for naphthalene (0.005–0.202 μg/L, n?=?16). On the other hand, plastic components were detected in 77 % of the samples. Most frequently detected compounds were dimethyl phthalate and benzophenone at concentrations of 0.005–0.125 (n?=?41) and 0.014–0.921 (n?=?32), respectively. Levels detected are discussed in terms of contamination origin and geographical distribution. Target compounds were detected at low concentrations. Results obtained showed the high quality of bottled water in the different countries around the world.     

Bioaccumulation and human health risk assessment of chromium and nickel in paddy rice grown in serpentine soils

The natural abundance of Cr and Ni in serpentine soils is well-known, but the food safety of rice grown in these hazardous paddy soils is poorly understood. The study evaluated the bioaccumulation of chromium (Cr) and nickel (Ni) in rice (Oryza sativa) grown in serpentine-derived paddy soils in the Philippines. Surface soil (0–20 cm) samples were collected and characterized across three (i.e., Masinloc, Candelaria, and Sta. Cruz) paddy areas in Luzon Island, Philippines. At least 3 to 4 whole rice plants at mature stage were uprooted manually in each sampling point where the soil samples were collected. The total Cr and Ni concentrations in rice (i.e., roots, shoots, and grains) and soil, soil physicochemical properties, bioaccumulation factor (BAF), translocation factor (TF), and the hazard quotients (HQ) were determined. Results revealed that Cr and Ni in rice were accumulated mostly in the roots. Although paddy soils had elevated total Cr and Ni concentrations, the BAF and soil-to-root TF values for Cr and Ni were < 1. In terms of human health risks, results further revealed low risk for both male and female Filipino adults as HQ values for Cr and Ni were < 1. While it is safe to consume rice grown in the area in terms of Cr and Ni dietary intake, more studies are necessary to understand the dynamics and bioavailability of these heavy metals in other crops and drinking water from tube wells in these areas in order to provide a more holistic human health-based assessments and to ensure consumer safety in serpentine areas. In addition, a more reliable data on Cr and Ni speciation in serpentine soils and crops is critically important. Further studies are also needed to understand the contribution of bioavailable heavy metals in improving the soil health to achieve food safety.

     

Stability considerations of aspartame in the direct analysis of artificial sweeteners in water samples using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

A HPLC-MS/MS method is presented for the simultaneous determination of frequently used artificial sweeteners (ASs) and the main metabolite of aspartame (ASP), diketopiperazine (DKP), in environmental water samples using the direct-injection (DI) technique, thereby achieving limits of quantification (LOQ) of 10 ng L⁻¹. For a reliable quantification of ASP pH should be adjusted to 4.3 to prevent formation of the metabolite. Acesulfame (ACE), saccharin (SAC), cyclamate (CYC) and sucralose (SUC) were ubiquitously found in water samples. Highest concentrations up to 61 μg L⁻¹ of ACE were found in wastewater effluents, followed by surface water with concentrations up to 7 μg L⁻¹, lakes up to 600 ng L⁻¹ and groundwater and tap water up to 70 ng L⁻¹. The metabolite DKP was only detected in wastewater up to 200 ng L⁻¹ and at low detection frequencies.     

Long-term effects of fertilization on the forms and availability of soil phosphorus in rice paddy

The changes in total P accumulation and P compounds with time in the plough layer in a paddy soil in southern Korea were investigated in relation to the continuous application of chemical fertilizers (NPK), straw based compost (Compost), combination these two (NPK+Compost) for 31 years. Continuous fertilization increased the total and inorganic P contents in plough layers. In NPK, inorganic P fraction did not change with time, but organic P content increased significantly. Long-term application of chemical fertilizer together with compost accelerated the decrease in the organic P fraction, presumably due to promoting microbial activity in the plow layer, and then increased significantly inorganic P fraction. Compost application decreased the residual P and Fe-P fractions and then increased inorganic P fraction, in spite of continuous compost application. Increase in total, inorganic and extractable P with time may be closely related to the increase in the availability of accumulated P for rice growth.     

Spatial distribution of heavy metals in rice grains and human health risk assessment in Hunan Province,China

Environmental Science and Pollution Research - Rice is the main food in China, and its pollution by heavy metals has attracted widespread attention. In this study, rice grain samples were collected...     

Determination of carbamazepine and 12 degradation products in various compartments of an outdoor aquatic mesocosm by reliable analytical methods based on liquid chromatography-tandem mass spectrometry

Environmental Science and Pollution Research - The aims of this work are to develop suitable analytical methods to determine the widely used anticonvulsant carbamazepine and 12 of its...     

Magnetic molecularly imprinted polymer prepared by microwave heating for confirmatory determination of chloramphenicol in chicken feed using high-performance liquid chromatography-tandem mass spectrometry

Abstract

A magnetic molecularly imprinted polymer (MMIP) for chloramphenicol was prepared using a surface-imprinted and microwave-heating-induced polymerization method. The surfaces of the magnetic particles were first double-bond functionalized with 3-(trimethoxysilyl)propyl methacrylate (γ-MPS), followed by the copolymerization of 4-vinyl pyridine (4-VP) and trimethylolpropane trimethacrylate (TRIM) in the presence of chloramphenicol as a template and 1,1-azobis(cyclohexane-carbonitrile) (ABCN) as an initiator in a mixture of dimethyl sulfoxide and water with microwave heating at 80°C. The magnetic polymer possesses supraparamagnetic properties and was used to concentrate and cleanup chicken feed extract, followed by chromatographic separation using a Lichrospher®100 RP C8 column and detection with two multi-reaction monitoring transitions at m/z 321→ 152 and m/z 321→ 257. The mean recoveries obtained at two spiking levels were in the range of 94.6–100% The relative intra- and inter-day standard deviations were in the range of 1.4–2.6% and 5.1–5.7%, respectively. The detection limit of the method was 0.12 µg kg^?1. This confirmatory method was successfully applied to determine chloramphenicol in chicken feed samples.     

The effect of water flooding at grain-filling stage on the uptake of heavy metal(loid)s by rice in slightly alkaline paddy soil

Environmental Science and Pollution Research - Continuous flooding has been widely used in paddy field to decrease the accumulation of heavy metal(loid)s by rice due to their decreased solubility...     

Simultaneous determination of organochlorine and pyrethriod pesticide residues in the Chinese patent medicines by gas chromatography-tandem mass spectrometry

A simple, sensitive, reliable method was developed for the simultaneous determination of organochlorine and pyrethriod pesticide residues in Chinese patent medicines Six ingredient rehmannia pills and Xiaoyao pills. These pesticides were extracted by ethyl acetate. The extraction time and volume of ethyl acetate were optimized. Cleanup of extracts was performed with dispersive-solid phase extraction using graphitized carbon black as the sorbent. The determination of pesticides in the final extracts was carried out by gas chromatography–tandem mass spectrometry in multiple reaction monitoring mode (GC-MS/MS, MRM). The linearity of the calibration curves is good in matrix-matched standard and yields the coefficients of determination (R²) ≥0.99 for all of the target analytes. Under optimized conditions, the average recoveries (five replicates) for most pesticides range from 75.5% to 114.6%, and RSDs are less than 10.0%. The LODs of 18 pesticides in Six ingredient rehmannia pill and Xiaoyao pills are in the range of 0.01–8.82 μg kg^?1. The developed method meets the requirements of pesticide residue analysis and could be effectively used for routine analysis of the organochlorine and pyrethriod pesticide residues in Six ingredient rehmannia pills and Xiaoyao pills.     

Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.     

Contamination and bioaccumulation of benzotriazole ultraviolet stabilizers in fish from Manila Bay, the Philippines using an ultra-fast liquid chromatography-tandem mass spectrometry

Methyl methacrylate (MMA) is grafted on multiwalled carbon nanotubes (MWCNTs) by using N₂ plasma technique. The MMA grafted MWCNTs (MWCNT-g-pMMA) are characterized by using Raman spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis-differential thermal analysis (TGA-DTA), and potentiometric acid-base titration method. The application of MWCNT-g-pMMA in the removal of 4,4′-dichlorinated biphenyl (4,4′-DCB) from large volumes of aqueous solutions is investigated under ambient conditions. The results indicate that the adsorption of 4,4′-DCB on MWCNT-g-pMMA is much higher than that of 4,4′-DCB on MWCNTs, and the adsorbed 4,4′-DCB is difficult to be thermally decomposed from MWCNT-g-pMMA according to the TGA-DTA analysis. MWCNT-g-pMMA are suitable materials in the preconcentration and immobilization of polychlorinated biphenyls (PCBs) from large volumes of aqueous solutions in environmental pollution cleanup.     

珠江三角洲潮土和水稻土酸缓冲特性试验研究

珠江三角洲潮土和水稻土对不同种类的酸具有一定的缓冲性,不同种类的酸对不同类型土壤的酸化趋势不同。大旺水稻土对酸的敏感性强于龙山潮土,龙山潮土属于稍易受害的稍敏感土壤,大旺水稻土属于易受害的敏感土壤;同一土壤对酸的缓冲能力比对碱的缓冲能力强;不同种类的酸对土壤的敏感性不同,土壤对硝酸的敏感性强于对硫酸的敏感性;土壤加酸后酸缓冲曲线和土壤中铝释放曲线的交点可以作为衡量土壤对酸敏感性的指标,交点越低,敏感性越强;加酸后土壤中铝的释放可以用模型y=nx+k来预测。     

Effect of applying persulfate on the accumulation of arsenic in rice plants grown in arsenic-contaminated paddy soil

Environmental Science and Pollution Research - Arsenic is known to be a notorious human carcinogen and rice consumption is becoming the primary human exposure route for As, especially in many Asian...     

浙江省饮用水源有机毒物污染特征及健康风险研究

在对浙江省98个县级以上饮用水源地水体中有机毒物污染进行调查的基础上,运用美国环境保护署(EPA)制定的相关模型对饮用水源地水体中有机毒物污染引起的健康风险进行评价。结果表明,在98个饮用水源地水体中共检出7种有机毒物,分别为微囊藻毒素-LR(MC-LR)、微囊藻毒素-RR(MC-RR)、草甘膦、邻苯二甲酸二异辛酯(DEHP)、邻苯二甲酸二丁酯、多环芳烃、咔唑;各饮用水源地水体中检出的有机毒物引起的健康风险大小依次为多环芳烃DEHP咔唑MC-LR草甘膦邻苯二甲酸二丁酯;存在有机毒物检出的饮用水源地水体的总健康风险约为10-13～10-8a-1,与部分国际机构制定的饮用水源地水质健康风险水平判断标准相比,浙江省饮用水源地水体中有机毒物污染引起的健康风险远低于可接受水平,大部分饮用水源地水体的健康风险甚至达到可忽略水平。     

Effects of rapeseed residue on lead and cadmium availability and uptake by rice plants in heavy metal contaminated paddy soil

Rapeseed (Brassica napus L.) has been cultivated for biodiesel production worldwide. Winter rapeseed is commonly grown in the southern part of Korea under a rice-rapeseed double cropping system. In this study, a greenhouse pot experiment was conducted to assess the effects of rapeseed residue applied as a green manure alone or in combinations with mineral N fertilizer on Cd and Pb speciation in the contaminated paddy soil and their availability to rice plant (Oryza sativa L.). The changes in soil chemical and biological properties in response to the addition of rapeseed residue were also evaluated. Specifically, the following four treatments were evaluated: 100% mineral N fertilizer (N100) as a control, 70% mineral N fertilizer + rapeseed residue (N70 + R), 30% mineral N fertilizer + rapeseed residue (N30 + R) and rapeseed residue alone (R). The electrical conductivity and exchangeable cations of the rice paddy soil subjected to the R treatment or in combinations with mineral N fertilizer treatment, N70 + R and N30 + R, were higher than those in soils subjected to the N100 treatment. However, the soil pH value with the R treatment (pH 6.3) was lower than that with N100 treatment (pH 6.9). Use of rapeseed residue as a green manure led to an increase in soil organic matter (SOM) and enhanced the microbial populations in the soil. Sequential extraction also revealed that the addition of rapeseed residue decreased the easily accessible fraction of Cd by 5-14% and Pb by 30-39% through the transformation into less accessible fractions, thereby reducing metal availability to the rice plant. Overall, the incorporation of rapeseed residue into the metal contaminated rice paddy soils may sustain SOM, improve the soil chemical and biological properties, and decrease the heavy metal phytoavailability.     

Effect of o-phenylenediamine on Cu adsorption and desorption in red soil and its uptake by paddy rice (Oryza sativa)

A study was carried out of Cu adsorption and desorption processes in red soil as affected by o-phenylenediamine (o-PD) in the range 0-80 mg/l. The results indicated that the presence of o-PD enhanced Cu adsorption in red soil in weakly acid media, meanwhile, desorption percentage of Cu from soil, extracted by 1.0 M MgCl(2), also increased when Cu adsorption in soil occurred in the presence of o-PD. The response of paddy rice to Cu in red soil shows that Cu toxicity was mitigated in the presence of o-PD and that the Cu concentration in rice straw decreased with increasing concentration of o-PD from 0 to 4.0 mmol/kg in soil. The fractions of background Cu in soil did not change noticeably in the presence of o-PD, whereas the effect of o-PD on the fractions of added Cu was significant. It was found that the exchangeable and carbonate bound Cu fractions decreased and the fraction of Cu bound to Fe-Mn oxides and organic matter increased with increasing o-PD concentration in soil when Cu was added at the same rate. Copper concentration in rice straw was significantly correlated with exchangeable Cu (r=0.961) and carbonate bound Cu (r=0.959) in soil. This result implicates that the behavior of Cu in soil is likely to be affected by organic pollutants containing amino groups.