土壤中总铬测定方法的比较研究

采用国标GB/T 17137-1997和GB/T 17141-1997中规定的两种方法即H2SO4-HNO3-HF、HNO3-HF-HClO4法对土壤样品进行消解处理,筛选了HNO3-HF-HClO4消化体系并进行改进,再运用火焰原子吸收分光光度法测定样品中总铬（Cr）的含量。结果表明：土壤总Cr测定中的3种预处理方法的测定结果存在明显差异,改进后的HNO3-HF-HClO4法优于原国标方法,该方法消解速度快（3 ~ 4 h）且完全,大大缩短了实验时间;该方法灵敏度高（最低检出限0.04 mg/L）、准确度高（相对误差在1.3% ~ 5.0%）、加标回收率高（94.6% ~ 108.7%）,精密度好（相对标准偏差小于5.7%）,是值得推广的土壤Cr消解方法,可应用于农业环境土壤质量样品的检测。     

不同前处理方法对秸秆金属元素原子吸收光谱分析结果的影响

秸秆中金属元素是关系农作物秸秆科学利用的重要组成部分,目前还没有统一的秸秆中金属元素原子吸收光谱(atomic absorption spectroscopy,AAS)测定方法标准,该研究采用原子吸收光谱测定黄芪(GBW10028)标准物质、玉米秸秆、小麦秸秆和棉花秸秆中金属元素含量,比较了不同前处理方法对样品中K、Cu、Fe、Zn和Mg分析结果的影响。结果表明:微波消解、干法灰化和湿法消解测定黄芪(GBW10028)标准物质中金属元素含量差异性显著(P<0.05),微波消解比干法灰化、湿法消解准确度高。微波消解对玉米秸秆、小麦秸秆和棉花秸秆中各金属元素的影响与黄芪(GBW10028)标准物质趋于一致。微波HNO3与微波HNO3-H2O2测定结果差异性不显著(P>0.05),微波HNO3比微波HNO3-H2O2和微波HNO3-H2SO4测定结果稳定。微波HNO3是进行秸秆样品金属元素含量测定时较准确简便的前处理方法。     

添加H2O2改性和HNO3/H2SO4改性生物质炭对一种酸性水稻土吸附Cd (Ⅱ)的影响

选择稻草、玉米秸秆和油菜秸秆作为制备生物质炭的原料，分别用H2O2和HNO3/H2SO4对生物质炭进行改性处理，以未改性的生物质炭和HCl处理的生物质炭作为对照。按土重3%的比例向采自安徽郎溪的酸性水稻土中添加上述生物质炭，在经历一个干湿交替周期后，进行Cd(Ⅱ)吸附/解吸实验，研究添加生物质炭对水稻土吸附Cd(Ⅱ)的影响及其机制。结果表明，两种改性方法均有效增加了生物质炭表面的质子结合位点数，且HNO3/H2SO4改性对生物质炭表面羧基官能团的扩增效果更显著。官能团的增加使得添加了HNO3/H2SO4改性生物质炭的水稻土对Cd(Ⅱ)的专性吸附能力显著增强。因此，添加HNO3/H2SO4改性生物质炭可以作为酸性水稻土吸附固定重金属Cd的一种新型方法。     

微波消解- 电感耦合等离子体质谱法测定有机肥中 镉、砷、汞、铅、铬含量

采用电感耦合等离子体质谱法（ICP-MS）测定,比较湿法消解30 min,湿法消解至近干和微波消解等不同前处理方法对有机肥料中镉、砷、汞、铅、铬元素的提取效果,建立了一种基于ICP-MS测定有机肥料多种重金属元素含量的方法。结果表明：湿法消解至近干和微波消解法对有机肥多元素成分分析标准物质（RMH-F001）中5项重金属含量的测试结果均满足标准要求,方法定量值、标准值偏差分别低于6.3%、5.7%;硝酸/过氧化氢体系-微波消解处理下,样品结果稳定性最佳,相对标准偏差为0.8%～6.8%,相对偏差为1.1%～9.0%,相对相差为2.2%～18.0%,加标回收率为99.4%～102.9%。硝酸/过氧化氢体系-微波消解-ICP-MS法可作为有机肥中5项重金属统一化测定的常规方法。     

微波消解-原子荧光法测定肥料中砷汞含量

建立了微波消解-原子荧光法同时测定肥料中砷和汞,进行消解条件、精密度、回收率等试验。方法显示,砷的检出限为0.014μg/L,汞的检出限为0.001 6μg/L,6次平行相对标准偏差<3%,3个水平的砷加标回收率90%~110%,汞加标回收率77%~83%。     

微波消解法测土壤中全磷和全钾

用微波消解法测定土壤标准样品、标准方法测定消解液P和K含量,通过实验确定最佳消解及分析条件;而且比较微波消解法和传统电热板消解法的精密度和准确度,建立微波消解技术测定土壤P和K前处理方法.结果表明:土壤样品用1∶1HNO3∶HF 10ml的混酸体系进行消解,效果最佳;对于土壤标样,微波消解法测定P和K的相对标准偏差分别为1.46%～3.20%和0.38%～0.84%,电热板消解法测定P和K的相对标准偏差分别为3.06%～4.15%和0.40%～2.08%,微波消解法的测出值均高于电热板消解法;微波消解法的准确度和重现性明显优于电热板消解法,与标准值的相对相差比较,微波消解法都低于5%;两种试验方法样品回收率测得为94%～105%,符合分析方法要求.方法快速简便并有较高准确度、精密度,值得推广和应用.     

微波消解-GFAAS测定肥料中铅、镉含量的方法

通过多个实验的研究分析建立了微波消解法作为样品前处理,原子吸收石墨炉(GFAAS)法同时测定肥料中铅、镉含量的方法。结果表明,铅的检出限为1.6μg/L,镉的检出限为0.11μg/L;7次平行相对标准偏差3%;3个浓度水平加标回收率均在90%～110%。微波消解-GFAAS法对肥料中铅镉测定结果准确、稳定,且更节约人力、物力以及时间,可作为推荐方法。     

微波消解—火焰光度法测定植物中全钾的研究

研究了采用HNO3—H2O2—HCl酸体系对植物样品进行微波消解,采用FP 640火焰光度计测定3种植物标准物质中全钾的含量。5个平行测定结果均在其证书标准值范围内,方法相对标准偏差为0.6%~1.6%,结果令人满意。     

碘化钾-甲基异丁基甲酮萃取电感耦合等离子体发射光谱法测定复合肥料中铊含量

建立了测定复合肥料中痕量铊的萃取电感耦合等离子体发射光谱法。该方法以王水消解样品,通过碘化钾-甲基异丁基甲酮(KI-MIBK)萃取富集铊元素,采用水平观测方式,以电感耦合等离子体发射光谱法进行测定。在 0～ 1.0 mg/L范围内,铊的质量浓度与积分面积线性关系良好( R2=0.9999),相对标准偏差为 2.32%(n=7),方法检出限为 0.014mg/kg,加标回收率在 90.6%～ 101%之间。     

国家标准《有机-无机复混肥料》中有机质测定方法的研究

用H2SO4—K2Cr2O7沸水浴法氧化有机碳,可避免尿素干扰,Cl 可定量扣除,有机碳氧化率为67%,回收率达99.23%,有机碳测定值的RSD为0.35～0.97%,可以满足测定要求。     

配位体交换在减慢由酸雨造成的可变电荷土壤酸化速度中的意义

For the purpose of evaluating the role of ligand exchange of sulfate ions in retarding the rate of acidification of variable charge soils,the changes in pH after the addition of different amounts of HNO3 or H2SO4 to representative soils of China were measured .A difference between pH changes caused by the two kinds of acids was observed only for variable charge soils and kaolinite,but not for constant charge soils and bentonite,The larger the proportion of H2SO4 in the HNO3-H2SO4 mixture,the lower the calculated H^ ion activities remained in the suspension.The difference in H^ ion activities between H2SO4 systems and HNO3 systems was larger for soils with a low base-saturation(BS) percentage than those with a high BS percentage.The removal of free iron oxides from the soil led to a decrease in the difference,while the coating of Fe2O3 on a bentonite resulted in a remarkable appearance of the difference.The effect of ligand exchange on the acidity status of the soil varied with the soil type.Surface soils with a high organic matter content showed a less pronounced effect of ligand exchange than subsoils did.It was estimated that when acid rain chiefly containing H2SO4 was deposited on variable charge soils the acidification rate might be slower by 20%-40% than that when the acid rain chiefly contained HNO3 for soils with a high organic matter content,and that the rate might be half of that caused by HNO3 for soils with a low organic matter content,especially for latosols.     

土壤消解方法研究及对上海浦东环境汞背景值初步调查

利用欧洲标准样作控制,对比研究了土壤总Hg测定的3种消解方法,并对浦东垃圾焚烧发电厂周围土壤总Hg的背景值进行了初步研究,结果发现浦东土壤Hg背景值达到192.68 ng/g,明显高于其它城市,这与上海的工业历史、农业施肥习惯有关,值得注意的是浦东地区土壤中的气态Hg(一个样品除外)含量都很高。     

含铁材料和稀土材料对矿区土壤As的固定效果

通过分析添加含铁材料（Fe2O3、Fe2（SO4）3）和稀土材料（CeCl3、LaCl3）后矿区污染土壤中交换态砷（As）含量和土壤pH值的变化规律,研究这2类材料对矿区土壤As的固定效果以及对土壤性质的影响。结果表明,Fe2O3对As固定效果不明显,当Fe2O3最大添加量为8g/kg（分别按Fe计）时,土壤中交换态As含量仅降低了3.81%,其他3种材料在本试验条件下表现出良好的效果,其中Fe2（SO4）3和LaCl3固定As的效果相当,CeCl3次之。当这3种材料的添加量分别为2,4,8g/kg（按Fe、La、Ce计）时,土壤交换态As含量无法检出。对土壤pH的测定发现,Fe2O3对土壤pH几乎没有影响,其他3种材料都不同程度降低了土壤pH,Fe2（SO4）3对土壤的酸化尤为明显,CeCl3和LaCl3对土壤的酸化强度相当。     

Screening method for determination of high levels of cadmium, lead, and copper in foods by polarized Zeeman atomic absorption spectrometry using discrete nebulization technique

A screening method for determination of cadmium, lead, and copper in foods was developed. The sample (1-3 g) is digested with HNO3-H2SO4-HClO4 in a centrifuge tube attached to a straight glass tube that prevents loss of HNO3 by volatilization. After digestion, potassium iodide, H2SO4, and MIBK (4-methyl 2-pentanone) are added, and the metals are extracted with MIBK as metal iodides. The MIBK solution is injected and the metals are determined by flame polarized Zeeman atomic absorption spectrometry using a discrete nebulization technique. Recoveries of metals from fortified milk powder, unpolished rice, fish, beef, peanut butter, apple, and cabbage were satisfactory. The analytical results for NBS Oyster Tissue and NIES Pepperbush, Chlorella, and Mussel agreed with certified or reference values except lead in Pepperbush. The limits of quantitation for cadmium, lead, and copper were 0.01, 0.09, and 0.02 ppm, respectively. This method is simple and safe for routine analysis of high levels of cadmium, lead, and copper in foods.     

用连续流动分析仪测定土壤微生物态氮的方法研究

本文在用连续流动分析仪 TRAACS2000测定土壤中常见十几种有机态氮化合物的基础上,对连续流动分析仪法和凯氏法测定土壤浸提液全氮和土壤微生物态氮的方法进行了比较研究。结果表明,连续流动分析仪所测标准有机态氮化合物的回收率平均为94%;连续流动分析仪测得浸提液中全氮量与凯氏定氮法所测浸提液中全氮量之间呈显著线性正相关;连续流动分析仪法测得的土壤微生物态氮与凯氏法测得的土壤微生物态氮的之间亦呈显著线性正相关,表明两种方法测得的氮来自土壤氮的同一组分,其转换系数分别为 Kn=0.48(CaCl2浸提) 或Kn=0.53(K2SO4浸提)。     

Determination of the chromium content in commercial breakfast cereals in Spain

Chromium (Cr) is an essential element, but the content of this element in many foodstuffs, including breakfast cereals, is still unknown. For this reason, the Cr content in different types of commercially available breakfast cereals in Spain (n = 36) was determined by GFAAS following acid mineralization using HNO(3)-H(2)SO(4)-HClO(4). On validation, the method yielded a recovery rate of 99 +/- 1.08%. Results indicated that breakfast cereals are rich in Cr, with contents ranging between 0.09 +/- 0.04 and 0.55 +/- 0.08 microg.g(-)(1) and a mean content of 0.23 +/- 0.12 microg.g(-)(1). Consumption of breakfast cereals by children and adolescents in Spain could supply a Cr intake of 6.9 microg/d, i.e., 3.45-13.8% of the ESSADI and 19.72% of the RDI.     

粤西黄铁矿区铊-铅污染土壤的环境质量研究

以云浮硫铁矿开采场和尾渣堆放区为研究对象,采用HNO3-H2O2-HClO4-HF混酸-微波消解处理土壤样品,运用电感耦合等离子体质谱（ICP-MS）测定土壤样品中重金属的含量,研究了开采场附近土壤表层、尾渣堆放区土壤剖面的铊、铅、镍、铜、锌、镉等毒害重金属的含量。结果表明,云浮硫铁矿开采活动给矿区土壤环境带来了严重的危害。与中国土壤环境背景值相比,土壤中重金属含量最高可为背景值的35倍。运用Muller地积指数对土壤重金属污染现状进行了系统的环境风险评估,证实目前云浮矿区土壤中存在不同程度的铊、铅、铜、锌、镉等毒害重金属污染,其中,铊、铅的污染最为严重,镉、锌等达到中度污染至强污染,且污染已经渗透至土壤深层,特别是毒害性极强的重金属铊,生态环境受到严重危害。     

Retention of heavy metals by carboxyl functional groups of biochars in small arms range soil

Long-term effectiveness of biochar for heavy metal stabilization depends upon biochar's sorptive property and recalcitrance in soil. To understand the role of carboxyl functional groups on heavy metal stabilization, cottonseed hull biochar and flax shive steam-activated biochar having a low O/C ratio (0.04-0.06) and high fixed carbon content (~80% dry weight basis) were oxidized using concentrated H(2)SO(4)/HNO(3) and 30% HNO(3). Oxidized and unoxidized biochars were characterized for O/C ratio, total acidity, pH, moisture, ash, volatile matter, and fixed carbon contents, Brunauer-Emmett-Teller surface area, and attenuated total reflectance Fourier transform infrared spectral features. Characterized biochars were amended (2%, 5%, 10%, and 20% in grams of biochar per gram of soil) on a sandy, slightly acidic (pH 6.27) heavy metal contaminated small arms range soil fraction (<250 μm) having low total organic carbon (0.518%) and low cation exchange capacity (0.95 cmol(c) kg(-1)). Oxidized biochars rich in carboxyl functional groups exhibited significantly greater Pb, Cu, and Zn stabilization ability compared to unoxidized biochars, especially in pH 4.9 acetate buffer (standard solution for the toxicity characteristic leaching procedure). Oppositely, only oxidized biochars caused desorption of Sb, indicating a counteracting impact of carboxyl functional groups on the solubility of anions and cations. The results suggested that appropriate selection of biochar oxidant will produce recalcitrant biochars rich in carboxyl functional groups for a long-term heavy metal stabilization strategy in contaminated soils.