Heavy metals in rice and garden vegetables and their potential health risks to inhabitants in the vicinity of an industrial zone in Jiangsu, China

Contamination of soil and agricultural products by heavy metals resulting from rapid industrial development has caused major concern. In this study, we investigated heavy metal (Cu, Zn, Pb, Cr, Hg and Cd) concentrations in rice and garden vegetables, as well as in cultivated soils, in a rural-industrial developed region in southern Jiangsu, China, and estimated the potential health risks of metals to the inhabitants via consumption of locally produced rice and garden vegetables. A questionnaire-based survey on dietary consumption rates of foodstuffs showed that rice and vegetables accounted for 64% of total foodstuffs consumed, and over 60% of rice and vegetables were grown in the local region. Average concentrations of Cr, Cu, Zn, Cd, Hg and Pb were 0.75, 2.64, 12.00, 0.014, 0.006 and 0.054 mg/kg dw (dry weight) in rice and were 0.67, 1.18, 4.34, 0.011, 0.002 and 0.058 mg/kg fw (fresh weight) in garden vegetables, respectively. These values were all below the maximum allowable concentration in food in China except for Cr in vegetables. Leafy vegetables had higher metal concentrations than solanaceae vegetables. Average daily intake of Cr, Cu, Zn, Cd, Hg and Pb through the consumption of rice and garden vegetables were 5.66, 16.90, 74.21, 0.10, 0.04 and 0.43 μg/(kg·day), respectively. Although Hazard Quotient values of individual metals were all lower than 1, when all six metal intakes via self-planted rice and garden vegetables were combined, the Hazard Index value was close to 1. Potential health risks from exposure to heavy metals in self-planted rice and garden vegetables need more attention.     

Effect of molecular weight of dissolved organic matter on toxicity and bioavailability of copper to lettuce

To clarify the e ects of molecular weight of dissolved organic matter (DOM) on the toxicity and bioavailability of copper (Cu) to plants, DOM extracted from chicken manure was ultra-filtered into four fractions according to their molecular weights by means of sequential-stage ultrafiltration technique. Lettuce seeds were germinated by being exposed to the solutions containing Cu2+ with or without di erent fractions of DOM. The concentration of copper in roots, leaves, sprouts and the length of roots were investigated. The results showed that not all fractions of DOM could improve copper availability or toxicity. The fraction of DOM with larger molecular weight more than 1 kDa had higher complexation stability with Cu2+ and caused lower concentration of free Cu2+ ion in the solution of copper plus the fraction, resulting in lower availability and toxicity of copper to lettuce, but the fraction with molecular weight less than 1 kDa had the opposite function. Therefore, the molecular weight of 1 kDa may be the division point to determine DOM to increase or decrease copper availability and toxicity.     

水环境中溶解性有机物溯源分析及分子结构表征概述

溶解性有机物(DOM)是地球上最大的碳基化合物反应性储层之一,涉及各种生物地化反应并且在污染物溶解度、毒性、生物利用度、流变性和分布中发挥重要作用。本文介绍了当前用于表征水环境中DOM的策略和工具,探讨了当前研究在技术限制(预处理过程复杂、仪器分辨率低、数据处理困)、结构复杂性、结构多变性等方面存在的诸多局限性。分析认为:已有研究主要侧重于溯源分析和分子结构特征解析,未来研究应该在不同的结构层面和角度开展,加强多学科融合、数据库创建、对照实验和协同工作。     

Application of nanoparticle tracking analysis for characterising the fate of engineered nanoparticles in sediment-water systems

Novel applications of nanotechnology may lead to the release of engineered nanoparticles (ENPs), which result in concerns over their potential environmental hazardous impact. It is essential for the research workers to be able to quantitatively characterise ENPs in the environment and subsequently to assist the risk assessment of the ENPs. This study hence explored the application of nanoparticle tracking system (NTA) to quantitatively describe the behaviour of the ENPs in natural sediment-water systems. The NTA allows the measurement of both particle number concentration (PNC) and particle size distribution (PSD) of the ENPs. The developed NTA method was applied to a range of gold and magnetite ENPs with a selection of surface properties. The results showed that the positively-charged ENPs interacted more strongly with the sediment than neutral and negatively-charged ENPs. It was also found that the citrate coated Au ENPs had a higher distribution percentage (53%) than 11-mercaptoundecanoic acid coated Au ENPs (20%) and citrate coated magnetite ENPs (21%). The principles of the electrostatic interactions between hard (and soft) acids and bases (HSAB) are used to explain such behaviours; the hard base coating (i.e. citrate ions) will interact more strongly with hard acid (i.e. magnetite) than soft acid (i.e. gold). The results indicate that NTA is a complementary method to existing approaches to characterise the fate and behaviour of ENPs in natural sediment.     

人工纳米颗粒在水体中的行为及其对浮游植物的影响

人工纳米颗粒(engineered nanoparticles,ENPs)因其特殊的尺寸效应及良好的光学、磁学等性质,已被广泛应用于医药、生物成像以及工业产品等领域.在生产、使用和排放的过程中,ENPs通过不同途径不可避免地进入水体,因此ENPs在水体中的行为和生物安全性也引起了人们的极大关注.在水生生态系统中,浮游植物作为初级生产者,为自身以及其他营养级生物提供营养物质、能量和氧气,因此受到ENPs的影响是难以估算的.近年来已有大量的研究证实ENPs对生物有毒性效应,但ENPs进入浮游植物体内的机制以及ENPs在浮游植物体内的生物运输和转化的报道较少,并且这方面的机制仍不甚明确.本文重点介绍了纳米材料进入水体的途径,在水体中的行为以及对浮游植物的生物效应的最新研究进展,但这方面的机制研究需要进一步深入.     

Understanding the risks of mercury sulfide nanoparticles in the environment: Formation, presence, and environmental behaviors

Mercury (Hg) could be microbially methylated to the bioaccumulative neurotoxin methylmercury (MeHg), raising health concerns. Understanding the methylation of various Hg species is thus critical in predicting the MeHg risk. Among the known Hg species, mercury sulfide (HgS) is the largest Hg reservoir in the lithosphere and has long been considered to be highly inert. However, with advances in the analytical methods of nanoparticles, HgS nanoparticles (HgS NPs) have recently been detected in various environmental matrices or organisms. Furthermore, pioneering laboratory studies have reported the high bioavailability of HgS NPs. The formation, presence, and transformation (e.g., methylation) of HgS NPs are intricately related to several environmental factors, especially dissolved organic matter (DOM). The complexity of the behavior of HgS NPs and the heterogeneity of DOM prevent us from comprehensively understanding and predicting the risk of HgS NPs. To reveal the role of HgS NPs in Hg biogeochemical cycling, research needs should focus on the following aspects: the formation pathways, the presence, and the environmental behaviors of HgS NPs impacted by the dominant influential factor of DOM. We thus summarized the latest progress in these aspects and proposed future research priorities, e.g., developing the detection techniques of HgS NPs and probing HgS NPs in various matrices, further exploring the interactions between DOM and HgS NPs. Besides, as most of the previous studies were conducted in laboratories, our current knowledge should be further refreshed through field observations, which would help to gain better insights into predicting the Hg risks in natural environment.     

Phytoremediation of engineered nanoparticles using aquatic plants: Mechanisms and practical feasibility

Certain plants have demonstrated the capability to take up and accumulate metals, thus offering the potential to remediate metal-contaminated water and sediment. Several aquatic species have further been identified which can take up metal and metal oxide engineered nanoparticles (ENPs). It is important to evaluate if aquatic plants exhibiting potential for metal phytoremediation can be applied to remediation of metallic ENPs. Understanding the interactions between ENPs and aquatic plants, and evaluating possible influences on metal uptake and phytoremediation processes is therefore essential. This review article will address the feasibility of green plants for treatment of ENP-affected aquatic ecosystems. Discussion will include common types of ENPs in current use; transformations of ENPs in aquatic systems; the importance of microorganisms in supporting plant growth; ENP entry into the plant; the influence of microorganisms in promoting plant uptake; and recent findings in phytoremediation of ENP-affected water, including applications to constructed wetlands.     

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV–visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV–visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca^2 + and Mg^2 +) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.     

Effects of dissolved organic matter from sewage sludge on sorption of tetrabromobisphenol A by soils

Sorption of tetrabromobisphenol A (TBBPA) by soil influences its fate and transport in the environment. The presence of dissolved organic matter (DOM) may complicate the sorption process in soil. The effects of DOM from sewage sludge on TBBPA sorption by three soils were investigated using batch equilibration experiments in the study. DOM was observed to be sorbed on the soils and the isotherms could be fitted by the Langmuir model. The effects of DOM on TBBPA sorption were dependent on the characteristics ...     

河流不同分子量溶解性有机质对全氟化合物赋存形态的影响

目前有关水体全氟化合物(PFASs)赋存特征的研究主要集中于总溶解态,对溶解性有机质(DOM)结合态PFASs的研究较为匮乏,尤其忽视了不同分子量DOM对PFASs赋存形态的影响. 为阐明河流上覆水体不同分子量DOM对PFASs赋存形态的影响,本文以长江干支流为例,分析了河流上覆水体11种典型PFASs (C4~C12)的浓度及组成,研究了不同分子量DOM结合态PFASs的赋存特征. 结果表明:①长江上覆水体中PFASs的平均浓度为52.6 ng/L,其中全氟戊酸(PFPeA)和全氟己酸(PFHxA)是最主要的单体污染物;由于受点源污染的影响,武汉段PFASs总溶解浓度及其单体浓度均显著高于其他采样点. ②长江上覆水体中DOM的浓度范围为0.08~3.84 mg/L (以C计),将水体DOM按分子量分离为<1 kDa、1~3 kDa、3~5 kDa、5~10 kDa和>10 kDa五种组分,各采样点中<1 kDa的溶解性有机碳(DOC)浓度(1.56~3.84 mg/L)显著高于其他分子量的DOC浓度. ③对于所检出的PFASs,<1 kDa DOM结合态PFASs (含自由溶解态)的浓度亦显著高于其他分子量DOM结合态PFASs的浓度,且其占水体总溶解态PFASs的比例均在85%以上,说明水体DOM结合态PFASs具有较高的生物有效性. 研究显示,水体不同分子量DOM结合态PFASs的赋存特征存在差异,因此对水体PFASs进行生态风险评价时需综合考虑不同分子量DOM结合态的含量及其生物有效性.      

Occurrence, polarity and bioavailability of dissolved organic matter in the Huangpu River, China

Dissolved organic matter （DOM） plays an important role in biogeochemical cycles in aquatic ecosystem. To investigate the characteristics of DOM in Huangpu River {the last tributary of the Yangtze River）, surface water samples were collected along the river from December 2011 to June, 2013. The concentrations of dissolved organic carbon （DOC）, the absorbance and fluorescence spectrum of DOM in water samples were measured. Fluorescent DOM in the Huangpu River was decomposed into four components by the parallel factor analysis （PARAFAC）, including one humic-like substance and three protein-like substances. It showed that high spatial variability of DOC concentration was observed in the upstream water compared to the downstream water, and so did the absorbance coefficients of chromophoric dissolved organic matter and the total fluorescence intensities of different PARAFAC components of DOM. Furthermore, there was a large difference between the polarity and bioavailability of DOM in the Huangpu River. Polar compounds dominated tyrosine-like component of fluorescent DOM in all seasons. Tryptophan-like and humic-like substances had more polar fraction in summer and autumn than those in winter, while aromatic protein-like materials had the highest polar fraction in winter. Almost all of fluorescent DOM components were refractory in spring, while less than 20% of fluorescent DOM in average were biodegradable within 4 weeks in other seasons. We concluded that the spatial variation in the abundance of DOM in the Huangpu River is mainly affected by the water discharges from the Hangjiahu Plain and the seasonal difference in polarity and bioavailability of DOM is largely determined by its origins.     

水环境中秸秆源溶解有机质的组成及光化学活性特征

利用紫外-可见吸收光谱、三维荧光光谱和稳态光化学反应技术,对水环境中水稻和小麦秸秆短期（91d）分解释放的溶解有机质（DOM）的组成、结构和光化学活性进行了研究.结果表明：在水环境中,秸秆分解释放DOM过程可分为物理淋溶、易分解组分分解和难分解组分分解三个阶段,其中易分解组分是该分解过程中秸秆DOM的主要来源;随分解周期增长,秸秆源DOM的芳香性、腐殖化程度及分子量不断增大,而生物可利用性逐渐减小;秸秆源DOM中的类酪氨酸、类腐殖酸和类富里酸在秸秆分解过程中逐渐累积,至分解末期,3种组分在水稻和小麦秸秆DOM中的含量分别增加了4.2%~14.3%和5.9%~12.8%,而类色氨酸和溶解性微生物分泌物相对不稳定,会被逐渐分解;秸秆源DOM的紫外和荧光光谱特征指数SUVA₂₅₄、E2/E3、S_275~295、S_R、BIX和FI均与其光生HO×、¹O₂和三线态DOM间具有良好的相关关系（r > 0.61,P < 0.05）,因此秸秆源DOM的光化学活性由其芳香结构、分子量及生物可利用性共同决定.鉴于此,研究认为,探讨生物可利用组分的光化学活性,及构建光谱特征指数预测DOM光化学活性的数学模型,是今后秸秆源DOM生态环境作用研究的两项重要内容.     

两种分子量分级下DOM的组分特征及其生物毒性

分别采用超滤离心管和超滤杯两种方式制备不同分子量的溶解性有机物（DOM）,探究不同的分子量分级方式对获得的DOM组成成分特征及其生物毒性效应的影响,同时判明各组分联合作用方式.DOM分别来源于城市污水厂出水（EfOM）及商品天然腐植酸（SWR-NOM）.结果表明,两种分级方式获得的不同分子量DOM含有相同的荧光峰,腐殖酸类物质是EfOM与SWR-NOM含有的主要荧光类有机质（FDOM）,占FDOM的56%~91%.同种DOM不同分子量组分中FDOM组成相对含量一致.采用超滤离心管分级得到的DOM在不同分子量区间内SUVA₂₅₄和E2/E3的差异较大,而采用超滤杯分级时差异变化较小.对于发光细菌急性毒性,在同一分子量区间内,采用超滤杯分级获得的DOM组分检测到的发光细菌毒性值大于采用超滤离心管分级检测到的结果,但采用超滤杯分级时<1kDa组分的急性毒性效应值低于检测限.利用浓度加和模型（CA）对DOM中各组分的联合作用方式进行判断,发现DOM混合物的联合毒性符合CA模型,预测联合毒性效应占检测到的实际水样毒性的67%~104%.     

Effect of dissolved organic matter on sorption and desorption of phenanthrene onto black carbon

Sorption and desorption of phenanthrene （PHE） onto black carbon （BC） extracted from sediments were studied in the presence of three types of dissolved organic matter （DOM）, including L-phenylalanine （L-PH）, peptone and citric acid. The nonlinearity of the sorption isotherms increased in the presence of DOM. The presence of L-PH reduced the sorption capacity and desorption hysteresis because of the solubilization of PHE in L-PH solution. Peptone at 50-500 mg/L also led to a decrease in sorption attributed to solubilization, although the sorbed peptone on the BC surface could slightly increase PHE sorption. Unlike L-PH and peptone, citric acid enhanced the sorption capacity and irreversibility of PHE on BC mainly due to the strong sorption of citric acid on the BC surface. Our results may help to understand the different impacts of DOM on the distribution and transport of PAH in the environment.     

Biochar affects methylmercury production and bioaccumulation in paddy soils: Insights from soil-derived dissolved organic matter

Biochar has been used increasingly as a soil additive to control mercury (Hg) pollution in paddy rice fields. As the most active component of soil organic matter, soil dissolved organic matter (DOM) plays a vital role in the environmental fate of contaminants. However, there are very few studies to determine the impact of biochar on the Hg cycle in rice paddies using insights from DOM. This study used original and modified biochar to investigate their effect on DOM dynamics and their potential impact on methylmercury (MeHg) production and bioaccumulation in rice plants. Porewater DOM was collected to analyze the variations in soil-derived DOM in paddy soils. The results showed that the addition of biochar, whether in original or modified form, significantly reduced the bioaccumulation of MeHg in rice plants, especially in hulls and grains (p<0.05). However, MeHg production in soils was only inhibited by the modified biochar. Biochar addition induced a significant increase in DOM's aromaticity and molecular weight (p<0.05), which decreased Hg bioavailability. Furthermore, enhanced microbial activity was also observed in DOM (p<0.05), further increasing MeHg production in the soil. Thus, the effect of biochar on the fate of Hg cycle involves competition between the two different roles of DOM. This study identified a specific mechanism by which biochar affects Hg behavior in rice paddy soil and contributes to understanding the more general influence of biochar in agriculture and contaminant remediation.     

Transport and humification of dissolved organic matter within a semi-arid floodplain

In order to understand the transport and humification processes of dissolved organic matter(DOM) within sediments of a semi-arid floodplain at Rifle,Colorado,fluorescence excitation–emission matrix(EEM) spectroscopy,humification index(HIX) and specific UV absorbance(SUVA) at 254 nm were applied for characterizing depth and seasonal variations of DOM composition.Results revealed that late spring snowmelt leached relatively fresh DOM from plant residue and soil organic matter down into the deeper vadose zone(VZ).More humified DOM is preferentially adsorbed by upper VZ sediments,while non-or lesshumified DOM was transported into the deeper VZ.Interestingly,DOM at all depths undergoes rapid biological humification process evidenced by the products of microbial by-product-like(i.e.,tyrosine-like and tryptophan-like) matter in late spring and early summer,particularly in the deeper VZ,resulting in more humified DOM(e.g.,fulvic-acid-like and humic-acid-like substances) at the end of year.This indicates that DOM transport is dominated by spring snowmelt,and DOM humification is controlled by microbial degradation,with seasonal variations.It is expected that these relatively simple spectroscopic measurements(e.g.,EEM spectroscopy,HIX and SUVA) applied to depth-and temporally-distributed pore-water samples can provide useful insights into transport and humification of DOM in other subsurface environments as well.     

重金属形态与生物毒性及生物有效性关系的研究进展

简要介绍了近年来环境化学中与生物毒性有关的重金属化学形态分析研究。同时归纳了环境因素对形态分布及生物毒性影响的研究进展,如何建立起形态和毒怀两者间的联系,即由物理化学测试给出生物毒性和生物有效性信息,是形态分析的发展方向,在形态与生物毒性上建立起飞析的水质标准,是目前研究的重点。     

Assessing the utility of dissolved organic matter photoreactivity as a predictor of in situ methylmercury concentration

Methylmercury(MeHg) bioaccumulation is a growing concern in ecosystems worldwide. The absorption of solar radiation by dissolved organic matter(DOM) and other photoreactive ligands can convert MeHg into less toxic forms of mercury through photodemethylation. In this study, spectral changes and photoreactivity of DOM were measured to assess the potential to control photoreactions and predict in situ MeHg concentration. Water samples collected from a series of lakes in southwestern Nova Scotia in June, August, and September were exposed to controlled ultraviolet-A(UV-A) radiation for up to 24 hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350 nm at constant UV-A irradiation, was positively dependent on the initial DOM concentration in lake waters(r~2=0.94). This relationship was consistent over time with both DOM concentration and photoreactivity increasing from summer into fall across lakes. Lake in situ MeHg concentration was positively correlated with DOM concentration and likely catchment transport in June(r = 0.77) but not the other sampling months. Despite a consistent seasonal variation in both DOM and Fe, and their respective correlations with MeHg, no discernable seasonal trend in MeHg was observed. However, a 3-year dataset from the 6 study lakes revealed a positive correlation between DOM concentration and both Fe(r = 0.91) and MeHg concentrations(r = 0.51) suggesting a more dominant landscape mobility control on MeHg.The DOM-MeHg relationships observed in these lakes highlights the need to examine DOM photoreactivity controls on MeHg transport and availability in natural waters particularly given future climate perturbations.     

基于土壤汞形态归趋的健康风险评估方法

土壤汞污染是一个全球性关注问题,矿产资源开采、化工生产和燃煤发电等均造成了不同程度的土壤汞污染,合理评估汞污染场地的健康风险是场地开发再利用的关键.对土壤中汞的形态归趋研究总结表明,由于汞的特殊物理化学性质,并受土壤等环境因素的影响,导致其在土壤中具有复杂的化学形态和变化过程.汞在土壤中的不同化学形态归趋对其毒性效应、生物有效性和暴露途径产生显著影响.基于土壤汞总量的风险评估方法忽略了土壤中不同化学形态汞对毒性、生物有效性和暴露途径的影响,导致高估土壤汞污染的健康风险.针对基于土壤汞总量的风险评估存在的问题,提出了基于土壤汞形态归趋的土壤汞污染健康风险评估理论,并构建基于土壤汞形态归趋-有效剂量-健康效应的土壤汞污染的精细化风险评估技术体系框架:①土壤不同形态汞的测定与表征方法;②汞形态归趋预测模型;③暴露分析与暴露量计算;④有效剂量（生物可给性或生物有效性）测定;⑤风险表征;⑥基于不同形态汞的场地土壤污染风险筛选值和修复目标制定.该方法体系从理论上解决了传统基于土壤汞总量的风险评估方法存在的问题,实际应用中面临的主要问题和今后重点发展方向:①研发可商业化的土壤汞化学物组分分析仪及土壤汞蒸气的原位测定方法;②结合中国场地土壤特点,开展土壤中汞的形态归趋模拟的模型研究,弥补现阶段土壤汞化合物形态分析方法的欠缺;③研发和建立土壤汞的生物可给性和有效性的标准测试方法技术;④本土化的土壤汞筛选值的确定.      

微生物降解影响下湖泊草源DOM与重金属的相互作用

通过微生物降解实验以及荧光滴定法研究草源溶解性有机质（DOM）光谱特性的不同以及铜（Cu）与草源DOM在微生物降解影响下的相互作用.三维荧光光谱结合PARAFAC分析显示,草源DOM含有3个荧光组分,新鲜的草源DOM以类蛋白质组分C2为主,微生物降解之后类腐殖质组分C1和C3成为草源DOM中的主要物质.二维相关光谱（2D-COS）,表明类蛋白物质在微生物降解过程中比类腐殖物质有着更高的敏感度和更快降解速率.并且随着Cu的增加,草源DOM中所有组分的荧光强度在微生物降解前后均发生明显猝灭.草源DOM原始样品中类腐殖质组分的络合常数大于类蛋白质组分,说明相比于类蛋白质组分,原始草源DOM中的类腐殖质组分有着更高的金属结合能力.而类蛋白质组分的络合常数在微生物降解之后的草源DOM中却高于类腐殖质组分.微生物降解对草源DOM的光谱特性以及金属结合能力有着显著影响,并对湖泊中重金属的生物有效性以及生态风险有着重要的意义.