高效液相色谱-电感耦合等离子体质谱测定大米粉中的硒形态

建立了高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定大米粉中硒代胱氨酸(SeCys_2)、甲基-硒代半胱氨酸(MeSeCys)、亚硒酸根(Se(Ⅳ))、硒代蛋氨酸(SeMet)、硒酸根(Se(Ⅵ))等5种硒形态的分析方法.采用Hamilton PRP-X100分析柱,以pH 4和pH 6的20 mmol·L~(-1)的柠檬酸溶液辅以少量甲醇为流动相,在梯度洗脱条件下,9 min内可实现5种硒形态完全分离.SeCys_2、MeSeCys、Se(Ⅳ)、SeMet、Se(Ⅵ)的检出限分别为0.88、0.69、1.00、0.90、0.82μg·L~(-1).利用富硒小麦粉标准物质RM8436探讨了不同提取方式的提取效果.最终确定75 mmol·L~(-1) Tris-HCl(pH 7.5)添加XIV蛋白酶和Driselase酶作为提取剂,在37℃振荡提取3 h为大米样品前处理方法.利用该方法分析了富硒地区大米粉中的硒形态,结果表明,大米粉中的硒主要以有机硒形态为主,其中SeMet是最主要的硒形态,占总硒的90%左右.     

山东省农田土壤中拟除虫菊酯类农药污染特征与风险评价

在山东省范围内采集农田表层土壤样品91个,采用气相色谱法分析了7种拟除虫菊酯类农药(SPs)的含量和组成,分析了其分布特征,比较了大田土壤和大棚土壤中该类农药含量的差异,并评价了其生态风险.结果表明,7种拟除虫菊酯类农药总含量(∑_7SPs)范围在0.01—88.51μg·kg~(-1)之间,均值为5.65μg·kg~(-1).与国内其他地区农田土壤相比,山东省农田土壤中拟除虫菊酯含量处于中等偏低水平.山东省各地区的拟除虫菊酯含量存在差异,但组成相近,均是高效氯氟氰菊酯、联苯菊酯和氯氰菊酯的比例较高.部分地区大棚土壤中的含量高于大田土壤.风险评价结果表明,山东省农田土壤个别采样点中甲氰菊酯和高效氯氟氰菊酯具有生态风险,三分之一的采样点存在潜在生态风险,其余采样点不存在生态风险.     

吹扫捕集/气相色谱-原子荧光光度法测定土壤和沉积物中烷基汞

本文将原子荧光光谱检测技术与吹扫捕集/气相色谱检测技术联用,结合优化的碱性法消解前处理技术,建立了碱性法消解-吹扫捕集/气相色谱-原子荧光光谱(PT-GC-AFS)联用技术测定土壤和沉积物中烷基汞含量的方法,能够在一次分析中同时获得样品中甲基汞和乙基汞的含量.本文分别用酸性法和碱性法处理了沉积物标准样品ERM-CC580、沉积物实际样品和土壤实际样品,重点比较了本方法提出的碱性法消解和使用率较高的酸性法消解两种前处理方式.采用本方法处理实际样品进行了色谱分离研究,对低浓度的实际土壤样品进行了检出限实验,用3种不同浓度的沉积物和3种不同浓度的土壤样品验证了精密度,对沉积物标准参考物质ERM-CC580进行了测定,并用两种实际土壤样品和两种实际沉积物样品进行了加标回收率试验.实验表明,碱性法消解精密度和准确度优于酸性法消解,且步骤少、耗时短,使用的试剂种类少、毒性小,方法稳定性高、可操作性强,适用于分析测试实验室大量土壤/沉积物样品的烷基汞测定.采用碱性法消解土壤/沉积物样品,目标物实现完全分离,甲基汞、乙基汞的线性相关系数分别为0.9999、1.0000,最低检出限分别为0.02μg·kg~(-1)、0.10μg·kg~(-1)(取样量为0.50 g),样品分析甲基汞、乙基汞的RSD范围分别为1.0%—4.7%、2.5%—6.0%,加标回收率范围分别为85.1%—109%、90.3%—96.3%.     

天津市地表水体与沉积物中7种高关注酚类化合物的污染特征与生态风险分析

为探究地表水体与沉积物中酚类化合物的污染分布特征和生态风险,选择天津市3个水源地与6条主要河流,采集了26个地表水样与6个沉积物样品,利用固相萃取与超声萃取、高效液相色谱-串联质谱法(HPLC-MS/MS)测定了水样及沉积物中1-萘酚(1-naphthol)、壬基酚(nonylphenol, NP)、双酚A(bisphenol A, BPA)、2-苯基苯酚(biphenyl-2-ol)、3,4-二氯酚(3,4-dichlorophenol)、四溴双酚A(tetrabromobisphenol A, TBBPA)和对叔丁基苯酚(p-tert-butylphenol, PTBP)等7种高关注酚类化合物的浓度水平,并应用物种敏感性分布(species sensitivity distribution, SSD)法和熵值法(ecological risk quotient, RQ)评估7种酚类化合物水环境和沉积物的生态风险。结果表明,地表水样中7种酚类化合物均全部检出;其中壬基酚的检出浓度最高,其次为四溴双酚A、对叔丁基苯酚、1-萘酚、2-苯基苯酚、3,4-二氯酚和双酚A。沉积物中酚类化合物的污染分布规律与水样相似,除双酚A外的目标物全部检出。其中,壬基酚浓度比其他物质浓度高2个数量级。风险评估结果显示,壬基酚对水环境与沉积物存在不可接受的风险;而四溴双酚A、对叔丁基苯酚、1-萘酚、2-苯基苯酚、3,4-二氯酚和双酚A则对环境具有较低风险或者存在一定的风险。     

典型有机磷酸酯阻燃剂分析方法研究进展

有机磷酸酯(OPEs)是一类重要的有机磷阻燃剂,近些年逐渐取代了溴代阻燃剂,广泛应用于各行各业,也因此导致在多种环境介质中有较高的暴露量和潜在风险。已有研究表明,OPEs具有一定的毒理效应,对人体及其他生物均有潜在危害。本文综述了近年来国内外OPEs的检测技术,详述了不同环境介质OPEs的前处理方法。结果表明,目前固相萃取(SPE)和固相微萃取(SPME)仍是水样前处理的主要方法;对于固体样品,加速溶剂萃取/加压液相萃取(ASE/PLE)和微波辅助萃取(MAE)应用较多;虽然大气样品仍以固体吸附剂方式为主,但已向在线一体化方向发展;而生物样品的前处理方法多与水样和固体样品方法相似;但是对于复杂环境介质中OPEs样品的前处理较为困难,方法有待改善;气相色谱-质谱联用(GC-MS)和气相色谱-氮磷检测器(GC-NPD)对弱极性和易挥发的OPEs分析效果好,而强极性和难挥发的OPEs多用液相色谱-质谱联用(LCMS);气相色谱-质谱串联(GC-MS/MS)、液相色谱-质谱串联(LC-MS/MS)和高效液相色谱-质谱串联(UPLC-MS/MS)等对多种复杂的环境介质中的OPEs均有较好的检测分析效果,但并未普及。最后,对OPEs分析测试方法的发展趋势提出了展望。     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

Photosynthesis and related metabolic mechanism of promoted rice (Oryza sativa L.) growth by TiO2 nanoparticles

• The rice growth was promoted by nano-TiO₂ of 0.1–100 mg/L. • Nano-TiO₂ enhanced the energy storage in photosynthesis. • Nano-TiO₂ reduced energy consumption in carbohydrate metabolism and TCA cycle. Titanium dioxide nanoparticle (nano-TiO₂), as an excellent UV absorbent and photo-catalyst, has been widely applied in modern industry, thus inevitably discharged into environment. We proposed that nano-TiO₂ in soil can promote crop yield through photosynthetic and metabolic disturbance, therefore, we investigated the effects of nano-TiO₂ exposure on related physiologic-biochemical properties of rice (Oryza sativa L.). Results showed that rice biomass was increased >30% at every applied dosage (0.1–100 mg/L) of nano-TiO₂. The actual photosynthetic rate (Y(II)) significantly increased by 10.0% and 17.2% in the treatments of 10 and 100 mg/L respectively, indicating an increased energy production from photosynthesis. Besides, non-photochemical quenching (Y(NPQ)) significantly decreased by 19.8%–26.0% of the control in all treatments respectively, representing a decline in heat dissipation. Detailed metabolism fingerprinting further revealed that a fortified transformation of monosaccharides (D-fructose, D-galactose, and D-talose) to disaccharides (D-cellobiose, and D-lactose) was accompanied with a weakened citric acid cycle, confirming the decrease of energy consumption in metabolism. All these results elucidated that nano-TiO₂ promoted rice growth through the upregulation of energy storage in photosynthesis and the downregulation of energy consumption in metabolism. This study provides a mechanistic understanding of the stress-response hormesis of rice after exposure to nano-TiO₂, and provides worthy information on the potential application and risk of nanomaterials in agricultural production.     

Metagenomic analysis reveals the effects of cotton straw–derived biochar on soil nitrogen transformation in drip-irrigated cotton field

Environmental Science and Pollution Research - Biochar has been widely accepted as a soil amendment to improve nitrogen (N) use efficiency, but the effect of biochar on N transformation metabolic...     

Manganese-modified biochar for highly efficient sorption of cadmium

Environmental Science and Pollution Research - In this study, corn stalk was modified by manganese (Mn) before (MBC1) and after (MBC2) pyrolysis at different temperatures (400~600 °C)...