Role of complex organic arsenicals in food in aggregate exposure to arsenic

For much of the world''s population, food is the major source of exposure to arsenic. Exposure to this non-essential metalloid at relatively low levels may be linked to a wide range of adverse health effects. Thus, evaluating foods as sources of exposure to arsenic is important in assessing risk and developing strategies that protect public health. Although most emphasis has been placed on inorganic arsenic as human carcinogen and toxicant, an array of arsenic-containing species are found in plants and animals used as foods. Here, we 2evaluate the contribution of complex organic arsenicals (arsenosugars, arsenolipids, and trimethylarsonium compounds) that are found in foods and consider their origins, metabolism, and potential toxicity. Commonalities in the metabolism of arsenosugars and arsenolipids lead to the production of di-methylated arsenicals which are known to exert many toxic effects. Evaluating foods as sources of exposure to these complex organic arsenicals and understanding the formation of reactive metabolites may be critical in assessing their contribution to aggregate exposure to arsenic.     

Thiolated arsenicals in arsenic metabolism: Occurrence, formation, and biological implications

Arsenic (As) is a notoriously toxic pollutant of health concern worldwide with potential risk of cancer induction, but meanwhile it is used as medicines for the treatment of different conditions including hematological cancers. Arsenic can undergo extensive metabolism in biological systems, and both toxicological and therapeutic effects of arsenic compounds are closely related to their metabolism. Recent studies have identified methylated thioarsenicals as a new class of arsenic metabolites in biological systems after exposure of inorganic and organic arsenicals, including arsenite, dimethylarsinic acid (DMAV), dimethylarsinous glutathione (DMAIIIGS), and arsenosugars. The increasing detection of thiolated arsenicals, including monomethylmonothioarsonic acid (MMMTAV), dimethylmonothioarsinic acid (DMMTAV) and its glutathione conjugate (DMMTAVGS), and dimethyldithioarsinic acid (DMDTAV) suggests that thioarsenicals may be important metabolites and play important roles in arsenic toxicity and therapeutic effects. Here we summarized the reported occurrence of thioarsenicals in biological systems, the possible formation pathways of thioarsenicals, and their toxicity, and discussed the biological implications of thioarsenicals on arsenic metabolism, toxicity, and therapeutic effects.     

Toxic metals in amniotic fluid and altered gene expression in cell-free fetal RNA

Both exposures to toxic metals, as well as deficiencies in essential metals, during pregnancy has been linked to a variety of negative reproductive outcomes. The exact etiologies of such outcomes and the effects of fetal exposure to these metals are largely unknown. Therefore, the ability to assess levels of these elements is critical to determining the underlying causes of such conditions and the effects that both essential and nonessential metals have on fetal development. Thus, using cell-free fetal RNA from amniotic fluid, we set out to measure the association between amniotic fluid levels of toxic and essential metals and fetal gene expression. We find that arsenic was associated with increased expression of 3 genes known to play roles in both birth-related and reproductive effects. The results highlight the potential for detrimental health effects of prenatal metals exposure and the potential to identify biomarkers of environmental exposure during this critical developmental period.     

我国东部沿海地区蔬菜中重金属累积分布特征及居民膳食暴露评估

采用电感耦合等离子体质谱仪（ICP-MS）分析了我国东部北方和南方沿海地区市售叶类、根茎类、瓜果类、豆类及食用菌5类蔬菜样品中6种有害金属元素（Cr、Ni、As、Cd、Hg和Pb）及5种人体必需金属元素（Mn、Fe、Cu、Zn和Se）的累积水平,并研究了其在不同蔬菜样品中的分布特征.结果表明,所有蔬菜样品中的6种有害金属水平均远低于国家食品安全标准规定的最高限量,居民食用这些蔬菜不存在明显的非致癌风险,但因食用蔬菜导致的无机砷暴露有10^-5水平的潜在致癌风险.蔬菜对有害金属和必需金属的累积呈现出明显的同步趋势（P<0.01）.相比其他蔬菜,食用菌表现出对有害金属及必需金属更高的累积水平,提醒人们需加强对食用菌中重金属污染的监测工作.     

焚烧厂周边居民重金属污染物多途径暴露的健康风险

焚烧厂排放的重金属污染物会通过不同途径富集于周围环境介质中,如土壤、地表水、地下水、大气、蔬菜和家禽等.焚烧厂周边人群通过上述各种环境介质暴露于重金属,并产生累计的健康危害.然而目前研究很少关注人群通过多途径暴露的累计健康风险.本研究调查了一座典型医疗废物焚烧厂周边不同环境介质中的重金属含量,分析其与人体暴露关系,并计算了其不同途径暴露的健康风险及累计风险.结果表明重金属产生的非致癌风险大小As(298.1)Cr(35.4)Mn(14.0)Pb(7.0)Cu(2.3)Hg(1.9)Zn(1),致癌风险大小依次为As(1.32×10-2)Cr(1.31×10-2)10-5,均超过风险可接受水平;食用自产蔬菜是主要的暴露途径(贡献率为68%~92%)其次为自养家禽贡献率为10%左右.这说明区别于通常关注的通过土壤、水体、空气等介质暴露的风险相比,食用研究区周边的动植物产品导致的风险更大,需要引起重点关注;不确定分析结果表明考虑污染物浓度不确定条件下,场地健康风险大约有0.54~2.28倍的增加;风险管理研究表明通过截断食用本地蔬菜和家禽,除Cr的致癌风险外,其他重金属对厂区居民的健康风险水平会迅速降低至可接受水平.     

环境水体中无机砷现场分析方法研究进展

砷是一种环境中普遍存在的类金属元素,并与人类健康息息相关.砷被列为一类致癌物,地下水中砷导致的慢性中毒是全球性健康问题.环境水体中砷的形态多样和毒性不尽相同,且在采样和运输过程中易于转化,而使实验室分析结果出现误差.因此开发砷的现场分析方法和获得准确的数据是研究砷的形态转化和生物吸收过程和准确判断其毒性的基础.在过去的几十年中,砷的实验室内分析方法迅速发展并逐渐成熟,但砷的现场分析仍然存在着巨大的困难和挑战.总结归纳了近10年来（2011~2022年）环境水体中砷分析方法相关的综述,讨论了砷的比色法、发光法和电化学法等现场分析方法的研究进展,并展望未来环境水体中砷现场分析方法的发展方向,为新方法的建立与应用提供参考.     

辽河铁岭段砷的人体健康水质基准研究

砷(As)是一种持久性、毒性强的致癌污染物。近年来我国As污染事件频发,故制定As的人体健康水质基准具有重要意义。以辽河铁岭段为研究对象,采集并分析水样和不同营养级的鱼样中As含量。结合文献调研,确定As的污染物毒性参数与辽河铁岭段饮水相关的部分人群暴露参数;基于线上问卷调查,计算本地居民人均第2、3、4营养级鱼类摄入量分别为0.0268,0.0323,0.0027 kg/d,进而推导出当地代表性鱼类As的第2、3、4营养级国家生物累积因子为8.256,9.281,10.197 L/kg。根据以上参数计算出辽河铁岭段As的人体健康水质基准值为1.976×10-5 mg/L,研究结果可为辽河流域制定水质标准提供参考,为更加科学有效地管控污染物排放和保护人体健康提供依据。     

Arsenic methylation by an arsenite S-adenosylmethionine methyltransferase from Spirulina platensis

Arsenic-contaminated water is a serious hazard for human health. Plankton plays a critical role in the fate and toxicity of arsenic in water by accumulation and biotransformation.Spirulina platensis(S. platensis), a typical plankton, is often used as a supplement or feed for pharmacy and aquiculture, and may introduce arsenic into the food chain, resulting in a risk to human health. However, there are few studies about how S. platensis biotransforms arsenic. In this study, we investigated arsenic biotransformation by S. platensis. When exposed to arsenite(As(Ⅲ)), S. platensis accumulated arsenic up to 4.1 mg/kg dry weight.After exposure to As(Ⅲ), arsenate(As(Ⅴ)) was the predominant species making up 64% to86% of the total arsenic. Monomethylarsenate(MMA(Ⅴ)) and dimethylarsenate(DMA(Ⅴ))were also detected. An arsenite S-adenosylmethionine methyltransferase from S. platensis(Sp Ars M) was identified and characterized. Sp Ars M showed low identity with other reported Ars M enzymes. The Escherichia coli AW3110 bearing Spars M gene resulted in As(Ⅲ) methylation and conferring resistance to As(Ⅲ). The in vitro assay showed that Sp Ars M exhibited As(Ⅲ) methylation activity. DMA(Ⅴ) and a small amount of MMA(Ⅴ) were detected in the reaction system within 0.5 hr. A truncated Sp Ars M derivative lacking the last 34 residues still had the ability to methylate As(Ⅲ). The three single mutants of Sp Ars M(C59S, C186 S, and C238S) abolished the capability of As(Ⅲ) methylation, suggesting the three cysteine residues are involved in catalysis. We propose that Sp Ars M is responsible for As methylation and detoxification of As(Ⅲ) and may contribute to As biogeochemistry.     

北京市居民膳食大米无机砷的暴露评估

砷（As）被世界卫生组织国际癌症研究机构列入Ⅰ类致癌物质.大米由于其组织特异性,更易于富集As,了解人群大米消费习惯,对评估大米As对人体健康危害具有重要意义.该研究对北京市人群大米暴露行为模式进行调查,并在北京市采集粳米、籼米、糯米和糙米4个种类的大米样品共160份.根据北京市人群的实际大米摄入量及不同种类大米的无机砷（iAs）含量,对人群不同种类大米As暴露浓度水平进行加权后开展大米iAs的精细化暴露评估.结果表明:①北京市居民消费的大米中iAs平均含量为0.060 mg/kg,低于GB 2762-2017《食品安全国家标准食品中污染物限量》中规定的大米As污染限值（0.2 mg/kg）,其中,粳米As含量（0.063 mg/kg）最高,籼米As含量（0.053 mg/kg）最低.②北京市居民每日大米摄入量为91.19 g,82.8%的居民以食用粳米为主.③北京市居民基于实际消费大米种类和大米摄入量评估的大米As暴露量为0.12 μg/（kg·d）,是未经加权评估的大米As暴露量的1.23~1.32倍,约占As允许摄入量[0.3 μg/（kg·d）]的40%.研究显示,北京市居民大米As暴露的健康风险处于可接受水平,精细化的暴露评估方法可减少暴露评估的不确定性.      

两个品种水稻对砷的吸收富集与转化特征及其健康风险

以2个水稻品种威优402号和Ⅱ优416号为实验材料,采用温室栽培方法研究对比两个品种水稻在人工添加砷处理(0、10、20和40mg·kg-1)和模拟自然砷污染(贵州高砷土和北京褐土的混合土,质量比为1∶1)胁迫条件下的生长发育状况,分析砷在水稻不同部位的累积、形态转化及其健康风险.砷处理显著地抑制了两个品种水稻的生长,水稻地上与地下部生物量、株高和穗数随砷处理水平的提高均出现明显的下降,但Ⅱ优416号的下降幅度明显低于威优402号.两个品种水稻籽粒中砷含量随砷处理水平提高也显著升高,人工添加砷各处理条件下,两个品种水稻稻谷中砷含量没有显著性差异;而在模拟自然砷污染土中,Ⅱ优416号稻谷中砷含量平均值为0.062mg·kg-1,明显低于威优402号稻谷平均值的0.278mg·kg-1.两个品种水稻各部位砷的转运系数在低砷处理时(10mg·kg-1)出现显著的升高,而在其他处理条件下保持不变.无论何种水稻品种,水稻各部位砷形态的组成和比例无显著性差异,水稻根、茎、叶中主要为无机砷,稻谷中无机和有机砷各占60%和40%.依据WHO相关建议标准,种植水稻品种Ⅱ优416号的健康风险要明显低于种植威优402号.     

武汉市城郊蔬菜种植区重金属积累特征及健康风险评价

为了解武汉市城郊蔬菜种植区土壤-蔬菜-地下水系统中重金属积累造成的健康风险,在武汉市城郊5个辖区内采集土壤、蔬菜、地下水样品,分析其中As、Cd、Hg、Pb 4种重金属的含量及积累特征;采用健康风险评价模型,并考虑区域人群特点及工作特性等进行参数优化,对研究区人群在不同暴露途径、不同暴露介质下的健康风险进行评价. 结果表明:土壤重金属单项污染指数呈Cd>As>Hg>Pb的分布特征,Cd、Hg的土壤累积指数分别为6.51、2.00;叶菜类、瓜果类、根茎类和豆类4个类别新鲜蔬菜中,叶类蔬菜的w(Pb)显著高于其他蔬菜种类,瓜果类的w(As)和w(Hg)相对较高,根茎类的w(Cd)最高;蔬菜-土壤、地下水-土壤系统中同种重金属元素含量存在较高的相关性;3种暴露介质下的健康风险水平表现为蔬菜>地下水>土壤,经口暴露风险占总个人年风险的98.90%;总个人年风险为1.97×10-5 a-1,其中致癌年风险占99.60%,该总个人年风险未超出国际辐射防护委员会(ICRP)推荐的最大可接受风险值(5.0×10-5 a-1),但要防止土壤-蔬菜-地下水系统的进一步污染.      

基于GIS矿区土壤重金属生态环境及人体健康评价

结合调整评估阈的潜在生态风险评估和符合我国人体暴露特征参数的人体健康风险评价法,对我国典型多金属矿区—苏仙区的土壤重金属污染进行评价,并利用GIS分析了潜在生态风险等级空间分布,探究了成人及儿童致癌及非致癌健康暴露风险.结果显示,土壤中砷(As)、汞(Hg)、铜(Cu)、铅(Pb)、锌(Zn)5种重金属含量均超出背景值,且单因子污染指数均大于1,综合污染指数达11.6.单因子潜在生态风险评价结果显示,全境内Zn和Cu处于轻微污染及以下;As污染呈西北(中度)—东南(强烈)污染风险走向,中度污染风险等级面积是强烈污染风险等级面积的2倍,空间上看,As的强烈风险区域覆盖柿竹园大型矿区位置;Pb在大型矿区位置周围形成面状3级(重度)污染风险区;整个研究区Hg潜在污染风险处于重度及以上等级.综合潜在生态风险评价结果显示,全境土壤污染主要以重度及强烈等级为主,高风险(强烈等级)区域在空间上覆盖柿竹园大型矿区所在地,并向东南方向面状延伸至研究区边界处.人体健康风险评价显示,针对成年群体,研究区存在显著综合非致癌健康暴露风险,其中,As对非致癌健康暴露风险的贡献最大;对于儿童群体,As、Pb的儿童非致癌健康暴露风险显著,手口摄入是这两种重金属儿童非致癌风险的主要暴露途径;致癌重金属As对成人不存在显著致癌风险,但儿童的致癌健康暴露风险显著.     

The dynamic changes of arsenic biotransformation and bioaccumulation in muscle of freshwater food fish crucian carp during chronic dietborne exposure

Dietary uptake is the major way that inorganic arsenic (iAs) enters into benthic fish; however, the metabolic process of dietborne iAs in fish muscle following chronic exposure remains unclear. This was a 40-day study on chronic dietborne iAs [arsenite (AsIII) and arsenate (AsV)] exposure in the benthic freshwater food fish, the crucian carp (Carassius auratus), which determined the temporal profiles of iAs metabolism and toxicokinetics during exposure. We found that an adaptive response occurred in the fish body after iAs dietary exposure, which was associated with decreased As accumulation and increased As transformation into a non-toxic As form (arsenobetaine). The bioavailability of dietary AsIII was lower than that of AsV, probably because AsIII has a lower ability to pass through fish tissues. Dietary AsV exhibited a high potential for transformation into AsIII species, which then accumulated in fish muscle. The largely produced AsIII considered more toxic at the earlier stage of AsV exposure should attract sufficient attention to human exposure assessment. Therefore, the pristine As species and exposure duration had significant effects on As bioaccumulation and biotransformation in fish. The behavior determined for dietborne arsenic in food fish is crucial for not only arsenic ecotoxicology but also food safety.     

Inorganic arsenic: A non-genotoxic carcinogen

Inorganic arsenic induces a variety of toxicities including cancer. The mode of action for cancer and non-cancer effects involves the metabolic generation of trivalent arsenicals and their reaction with sulfhydryl groups within critical proteins in various cell types which leads to the biological response. In epithelial cells, the response is cell death with consequent regenerative proliferation. If this continues for a long period of time, it can result in an increased risk of cancer. Arsenicals do not react with DNA. There is evidence for indirect genotoxicity in various in vitro and in vivo systems, but these involve exposures at cytotoxic concentrations and are not the basis for cancer development. The resulting markers of genotoxicity could readily be due to the cytotoxicity rather than an effect on the DNA itself. Evidence for genotoxicity in humans has involved detection of chromosomal aberrations, sister chromatid exchanges in lymphocytes and micronucleus formation in lymphocytes, buccal mucosal cells, and exfoliated urothelial cells in the urine. Numerous difficulties have been identified in the interpretation of such results, including inadequate assessment of exposure to arsenic, measurement of micronuclei, and potential confounding factors such as tobacco exposure, folate deficiency, and others. Overall, the data strongly supports a non-linear dose response for the effects of inorganic arsenic. In various in vitro and in vivo models and in human epidemiology studies there appears to be a threshold for biological responses, including cancer.     

不同电子废弃物拆解场重金属经口暴露的健康风险研究

以浙江台州电子废弃物拆解区为研究区域,采用现场调查和实验室分析相结合的方法对不同拆解场(焚烧场、手工拆解场、酸洗场)各环境介质中Cu、Pb、Cd等共7种重金属的污染状况进行调查,运用美国环保局健康风险评价模型对不同场地的人群经口暴露的健康风险进行评估,并通过调查问卷、实测等方式优化了暴露参数.研究结果表明:3个拆解场经口暴露的风险度均超过国际组织推荐的可接受风险水平,其中:手工拆解场的致癌风险度最大,焚烧厂的非致癌风险水平最高.从暴露途径角度分析,食物摄入的致癌风险水平最高,地下水经口摄入的非致癌风险水平最高;从元素角度分析,As的致癌风险水平最高,Cr的非致癌风险度最大.敏感性分析表明:实测参数体重(BW)对健康风险具有负敏感性,约为14%～15%,污染物浓度(C)、摄入率(IRw、IRF、IRs)具有正敏感性,分别为15%～16%和15%.     

高原湖泊砷污染健康风险评估

以某高原湖泊为例,以湖水中的砷含量类比推算了从该湖泊取水灌溉区域内水稻和蔬菜的砷含量,对稻米、蔬菜和饮水3种暴露途径进行健康风险评估。结果表明,人群通过摄入区域内稻米、蔬菜的致癌风险系数为可接受的致癌风险,饮用湖水的致癌风险系数为不可接受的致癌风险。     

科学识别环境健康传导链的六大特征

区域环境污染情景特点决定了环境健康传导链的具体特征,不同环境污染情景下环境健康传导链在目标污染物、目标区域、主要介质、潜在暴露途径、目标人群、健康效应等六个方面具有显著的差异.科学识别环境健康传导链的六大特征是环境污染情景分析和识别具体区域环境健康问题特征的关键环节,是制定环境健康危害调查技术方案和解决环境健康问题的技术基础.     

电子废弃物拆解场多氯联苯含量及健康风险评价

选择我国典型的电子废弃物拆解场为研究对象,以拆解场各环境介质中PCBs浓度全面调查为基础,采用美国环境保护署(US EPA)人体健康评价模型,结合问卷调查和实际测量修正暴露参数,对浙江台州拆解区人群(成人)进行健康风险评价.结果表明:拆解场大气和土壤中PCBs各同系物的浓度显著高于其他介质,经调查表明可能与拆解场直接焚烧、湿法酸洗工艺有关.多种暴露途径所导致拆解场成人PCBs污染总致癌风险为2.80×10-3,总非致癌风险为1.64×10-3,均超过了US EPA、ICRP等推荐的可接受的风险水平,其中经口暴露的致癌、非致癌风险最大,其次是呼吸暴露.进行敏感性分析表明:无论何种暴露途径,体重(BW)、呼吸速率(IR)、实测参数食物摄食(IR)、皮肤接触表面积(SA)和污染物实测浓度的致癌风险、非致癌风险绝对敏感性都较大.在健康风险评价时,需要对研究区人群暴露参数进行实地调查实测,以降低评价结果的不确定性.     

贵阳主要城区市售食用菌中重金属污染与健康风险评估

食用菌是一类绿色保健食品,但对重金属具有一定的富集能力.本文从贵阳市主城区农贸市场、大型超市分期采集了各类食用菌共计153份,分析检测了其中的As、Cd、Cr、Cu、Hg、Mn、Pb、Sb、Se、Tl和Zn等11种重金属元素含量.结果表明:本次样品中Cd元素超标频次最高,其次为As、Pb和Hg元素;重金属元素在干制品姬...