河北省典型污灌区农田镉污染特征及环境风险评价

以河北省石家庄市典型历史污灌区农田为研究对象,对污灌区内土壤和小麦、玉米植株内Cd的含量进行分析,评价污灌区农田Cd污染程度、潜在生态风险和潜在健康风险.结果表明,上游污灌区和中下游污灌区土壤表层Cd含量分别为ND～3.88、0.10～2.30 mg·kg~(-1),明显高于清灌区(0.13～0.23 mg·kg~(-1))及河北土壤背景值(0.094 mg·kg~(-1)),超农用地土壤污染风险筛选值(0.3 mg·kg~(-1))点位分别达42.9%和35.2%;小麦和玉米籽粒平均Cd含量均未超标,小麦籽粒富集浓度高于玉米,污灌区小麦和玉米籽粒已出现明显累积现象.潜在生态风险表明上游污灌区和中下游污灌区表层土壤基本处于轻度～中度风险,部分区域生态风险较高～极高.健康风险评价结果表明Cd通过皮肤、呼吸、经口摄入暴露途径对人体健康造成的风险在可接受范围内.研究结果为污灌区农田土壤的安全利用和管理决策依据,并为开展农田土壤修复工程提供科学参考.     

Toxicity and subcellular distribution of cadmium in wheat as affected by dissolved organic acids

We aim to investigate the effects of humic acid (HA) and citric acid (CA) on the toxicity and subcellular distribution of Cd in wheat. Results show that the toxicity and uptake of Cd decreased with increasing HA. The EC₅₀ values of Cd increased from 3.36 μmol/L to 4.96 and 7.33 μmol/L at 50 and 250 mg/L HA, respectively, but decreased to 1.39 μmol/L in the presence of CA based on free ion activity model (FIAM). HA decreased the relative subcellular distribution of Cd in the heat-denatured proteins (decreased from 54% to 33%) but increased Cd in the heat-stable proteins in root (from 25% to 50%) at 7.61 μmol/L {Cd²⁺} (free Cd activity), which resulted in decreasing Cd toxicity. However, CA increased Cd toxicity due to the increased internalization of Cd although the relative subcellular distributions of Cd exhibited a decrease in the heat-denatured proteins and increase in the granule fraction compared to the control at high-level Cd. The FIAM could not predict the toxicity of Cd in the presence of organic acids. Alternatively, the internal Cd accumulation and subcellular Cd concentration were better to describe the toxicity of Cd to wheat.     

玉米秸秆生物炭对稻田土壤砷、镉形态的影响

通过室内土壤培养的方法模拟稻田土壤环境,研究淹水环境下添加(1%添加量)不同温度制备的玉米秸秆生物炭(CB-300、CB-400、CB-500)对砷、镉复合污染稻田土壤氧化还原电位(Eh)、pH值及不同形态砷、镉含量动态变化的影响.结果表明,热解温度会影响玉米秸秆生物炭的理化性质,热解温度由300℃升至500℃,玉米秸秆生物炭芳香性增加,亲水性和极性降低,灰分含量增加,pH值升高.淹水环境下添加玉米秸秆生物炭处理相比对照(CK)可提高土壤pH值0.20~1.24,升高幅度大小为CB-500CB-400CB-300CK,随着培养时间的延长,pH值趋于平衡状态;淹水环境下土壤氧化还原电位均迅速下降,且不同处理组间存在显著差异,生物炭制备温度越高下降效果越明显,培养至第96 d时氧化还原电位降到最低.CK、CB-300、CB-400、CB-500处理组弱酸可提取态镉含量由淹水前的73.55%分别降至63.46%、57.73%、54.50%、53.94%,随着培养时间的延长,土壤中弱酸可提取态及可氧化态镉逐渐向残渣态及可还原态镉转化.土壤pH值与弱酸可提取态镉含量之间呈显著负相关关系.淹水环境下土壤可交换态砷含量升高,玉米秸秆生物炭的施加导致土壤交换态、Ca-结合态、Al-结合态和Fe-结合态砷含量逐渐上升,上升幅度分别为75.68%、20.92%、13.49%、48.66%,残渣态砷含量下降;土壤pH值与交换态砷含量之间呈显著正相关关系.研究结果可为砷、镉复合污染稻田安全生产与阻控提供数据支持.     

广西高镉异常区水田土壤Cd含量特征及生态风险评价

本研究调查了广西高镉异常区水田土壤中重金属Cd的含量水平,评估其对环境的潜在生态风险.通过初步筛查和详细调查两部分,分批次采集高镉异常区土壤样品共912件,测定土壤Cd含量,并运用单因子污染指数法和潜在风险指数法对水田土壤Cd污染程度及潜在风险进行评价.结果表明:①初查中自然土壤、水田土壤和旱地土壤Cd几何均值分别为0. 915、0. 591和0. 593 mg·kg~(-1).②详查中土壤p H为4. 6～8. 7,介于酸性和弱碱性间.若以《土壤环境质量标准》(GB15618-2018)为标准,平果县、天等县、大新县、隆安县和柳城县水田土壤样点Cd超标严重,融水县水田土壤样点无污染;以土壤基线值为评价标准,田东县、柳城县和融水土壤样点中Cd均为无污染状态;田阳县、平果县、天等县、大新县、隆安县和融安县水田土壤Cd处于轻度-中度污染的比例分别为:4. 2%、3. 7%、14. 9%、2. 6%、7. 1%和1. 4%.③9个县市水田土壤中Cd呈现不同级别潜在生态风险.天等县、大新县和隆安县部分水田土壤样点Cd处于高等生态风险,比例为4. 3%、2. 6%、2. 4%;田阳县、平果县、融安县和柳城县水田土壤Cd表现为中-中高等潜在风险;田东县和融水县处于低潜在生态风险.总体上,研究区水田土壤中Cd整体偏高,长此以往可能会对水稻安全种植产生影响,最终对当地居民产生健康威胁,应引起重视.建议开展对研究区土壤镉生物有效性和水稻镉累积状况研究,以便科学合理地评估其生态风险和健康风险.     

嗜麦芽窄食单胞菌对铜镉的吸附特性与离子交换

研究了投菌量、金属浓度和戊二醛浓度对嗜麦芽窄食单胞菌吸附水体中Cu2+和Cd2+特性的影响,分析了重金属生物吸附、NO3-去除与菌体离子释放的关联,从离子吸附、交换、转化与释放的角度探讨了重金属生物吸附机制.结果表明嗜麦芽窄食单胞菌对Cu2+和Cd2+吸附性能良好,0.2 g·L-1干重菌体处理浓度为0.05 mmol·L-1的Cu(NO3)2和Cd(NO3)2溶液120 min后,Cu2+和Cd2+的吸附率分别达96.3%和83.9%.菌体对Cu(NO3)2和Cd(NO3)2溶液的吸附过程存在Cu2+和Cd2+的表面吸附与胞内运输、NO3-胞内积累、NO3-还原为NO2-等行为,而且Cu2+和Cd2+的胞内运输、NO3-积累和还原需要消耗能量,并会促进Cl-、PO43-、SO42-、Na+、NH4+、K+和Ca2+等离子的释放.红外光谱分析表明菌体酰胺基、羟基与羧基均参与了Cu2+和Cd2+的吸附.X-光电子能谱分析显示吸附后Cu2+和Cd2+的价态不发生变化.     

Removal of Cd2+ from water by Friedel’s salt (FS: 3CaO.Al2O3·CaCl2·10H2O): Sorption characteristics and mechanisms

The development of low-cost and efficient new mineral adsorbents has been a hot topic in recent years. In this study, Friedel’s salt (FS:3CaO·A12O3 ·CaCl2 ·10H2O), a hexagonal layered inorganic absorbent, was synthesized to remove Cd2+ from water. The adsorption process was simulated by Langmuir and Freundlich models. The adsorption mechanism was further analyzed with TEM, XRD, FT-IR analysis and monitoring of metal cations released and solution pH variation. The results indicated the adsorbent FS had an outstanding ability for Cd(Ⅱ) adsorption. The maximum adsorption capacity of the FS for Cd(Ⅱ) removal can reach up to 671.14 mg/g. The nearly equal numbers of Cd2+ adsorbed and Ca2+ released demonstrated that ion-exchange (both surface and inner) of the FS for Cd(Ⅱ) played an important role during the adsorption process. Furthermore, the surface of the FS after adsorption was microscopically disintegrated while the inner lamellar structure was almost unchanged. The behavior of Cd(Ⅱ) adsorption by FS was significantly affected by surface reactions. The mechanisms of Cd2+ adsorption by the FS mainly included surface complexation and surface precipitation. In the present study, the adsorption process was fitted better by the Langmuir isotherm model (R2 = 0.9999) than the Freundlich isotherm model (R2 = 0.8122). Finally, due to the high capacity for ion-exchange on the FS surface, FS is a promising layered inorganic adsorbent for the removal of Cd(Ⅱ) from water.     

Simultaneous preconcentration of cadmium and lead in water samples with silica gel and determination by flame atomic absorption spectrometry

A new method that utilizes pretreated silica gel as an adsorbent has been developed for simultaneous preconcentration of trace Cd(II) and Pb(II) prior to the measurement by flame atomic absorption spectrometry. The effects of pH, the shaking time, the elution condition and the coexisting ions on the separation/preconcentration conditions of analytes were investigated. Under optimized conditions, the static adsorption capacity of Cd(II) and Pb(II) were 45.5 and 27.1mg/g, the relative standard deviations were 3.2% and 1.7% (for n = 11), and the limits of detection obtained were 4.25 and 0.60 ng/mL, respectively. The method was validated by analyzing the certified reference materials GBW 07304a (stream sediment) and successfully applied to the analysis of various treated wastewater samples with satisfactory results.     

浙中某县Cd元素地球化学特征及生态效应

本文基于对浙中某县土壤-作物系统的调查研究,系统总结了Cd元素地球化学特征。研究发现,土壤中Cd含量呈现表层富集趋势;土壤Cd元素的赋存形态以离子交换态为主,占各形态总量比例高达39.68%,显示出该地区土壤中Cd的活性相对较强;Cd污染区在南部山区沿水系分布,在研究区北部零星分布。研究同时发现,污染主要是由于矿山开采、工业废物排放以及污水灌溉等人类活动引起,并且污染区已出现稻米样品Cd超标,应引起有关部门足够重视。     

高镉地质环境富硒土壤特征及其生态效应

文章详细研究了浙西富硒土壤中Cd、Se、Zn、Ni存在形态以及农产品安全性。结果表明,研究区土壤继承了成土母质中硒、镉高含量的特点,引起农产品中富硒和镉含量超标。研究发现,当地居民并未由于农产品镉超标而出现群体性疾病,相反地,则表现为体格健壮,长寿老人较多,人发中镉含量低,硒含量高等特点。优良的生态现象可能与人体内Zn、Se对Cd的拮抗作用有关。这一研究结果,为黑色岩系地区富硒土壤的深层次开发利用提供了思路和机遇。     

Cd污染土壤的植物修复研究进展

我国农业土壤重金属污染十分严重,在所有的重金属污染中,Cd以其移动性大、毒性高成为最受关注的重金属污染之一。修复Cd污染的土壤,已成为我国农业可持续发展亟待解决的问题。与传统环境修复技术相比,植物修复技术治理成本低廉,土壤破坏力小,安全性高,是目前发展最快的环境友好、经济、高效的治理技术。介绍了Cd污染现状、超积累植物的概念和特征、土壤重金属污染植物修复国内外研究进展,并对其发展趋势进行了分析。