气相色谱法同时测定蔬菜中醚菌酯和肟菌酯残留量的方法研究

建立了一种同时测定蔬菜中醚菌酯和肟菌酯农药残留的气相色谱法。以乙腈高速匀浆提取、盐析,再经氟罗里硅土柱层析、净化,再经浓缩、定容后,采用气相色谱-电子捕获检测器对待测组分进行了分离和测定。本实验选用番茄为实验原料,通过在番茄样品中添加不同浓度的醚菌酯和肟菌酯混合标样,每档浓度做5个平行和1个空白。实验证明,添加浓度在0.01mg·kg-1、0.05mg·kg-1和0.2mg·kg-1时,番茄中醚菌酯和肟菌酯添加回收率在81.2%～106.5%之间,相对标准偏差(RSD,n=5)小于10%,醚菌酯和肟菌酯在样品中的最低检出浓度为0.005mg·kg-1。     

大米蛋白的酶水解动力学研究

以米渣为材料,研究碱性蛋白酶、1398中性蛋白酶和木瓜蛋白酶在不同起始pH值、加酶量和温度下水解大米蛋白的进程,建立大米蛋白酶水解动力学方程,为大米蛋白酶水解特性的研究提供依据.在一级化学反应动力学方程基础上,建立了考虑温度、起始pH值和加酶量影响的大米蛋白酶水解动力学模型,该模型可较好的描述不同蛋白酶对大米蛋白的水解进程.木瓜蛋白酶适于在较低的起始pH值下水解,加酶量、起始pH值对其水解进程的影响较大,温度变化对其水解进程的影响较小.1398中性蛋白酶适于在中性条件下水解,加酶量和水解温度对其水解进程的影响程度处于木瓜蛋白酶和碱性蛋白酶之间,起始pH值变化对其水解进程的影响不大.碱性蛋白酶适于在较高pH值下水解,加酶量对其水解进程影响不大,温度的变化对水解进程影响较大.     

啶氧菌酯环境归趋与生态风险研究进展

啶氧菌酯是一种对生态系统存在安全风险的甲氧基丙烯酸酯类杀菌剂,从环境归趋,生态毒理的角度出发,综述了啶氧菌酯在土壤、水中、农作物中的归趋,阐述了啶氧菌酯对蚯蚓、蜜蜂和水生非靶标生物急/慢性毒性,和对组织、酶活、蛋白、基因等方面的影响进行了归纳,并讨论了啶氧菌酯未来的生态毒理学研究方向。以期为进一步研究啶氧菌酯对非靶标生物毒性效应和作用机理,并制定相关策略以减少其生态风险提供依据。     

蛋白质水解度的简易测定方法

介绍了一种比较简单可行的蛋白质水解度的测定方法，该方法基于国外通用的pH-STAT法，不需要特别的仪器，化学试剂耗量少，测定结果可靠，便于实验室和工业化生产使用。     

嘧菌环胺·异菌脲可湿性粉剂在葡萄和土壤中的残留消解动态及风险评估

通过对嘧菌环胺·异菌脲可湿性粉剂在葡萄和土壤中开展两年两地的残留消解和最终残留试验,旨在为该农药在生产上的使用及有效控制提供合理数据。本文依据《农药残留试验准则》设计田间试验方案并实施,利用气相色谱-三重四极杆串联质谱(GC-QqQ-MS/MS)对葡萄和土壤样品中的嘧菌环胺和异菌脲进行检测,对残留量用农药风险商和危险商公式计算。结果显示,嘧菌环胺在葡萄和土壤中的消解半衰期是6.6~11.2 d,异菌脲在葡萄和土壤的半衰期是1.7~18.7 d。结果表明,当采收间隔期7 d时,嘧菌环胺和异菌脲的残留量均低于我国规定的最大残留限量值,其风险商和危险商均小于100%,在可控风险范围之内。因此,嘧菌环胺·异菌脲可湿性粉剂在葡萄的生产中使用是安全的。     

温度和pH值对雷克拉水解速率的影响

通过室内模拟研究的方法,试验探讨了温度,ｐＨ值对雷克拉在水溶液中水解速率的影响。结果表明,随着温度和ｐＨ值的升高,其降解速率也随之明显增大。     

新型杀菌剂唑菌酯在黄瓜植株中的动态代谢

唑菌酯是我国创制的具有完全自主知识产权的一种新型高效杀菌剂.本文以14C放射性标记唑菌酯为示踪剂,在实验室条件下,研究了唑菌酯在黄瓜植株中的动态代谢变化及其规律.结果表明:(1)施药后,黄瓜植株对唑菌酯的吸收呈随时间推移而增加的趋势,至12d时黄瓜植株对唑菌酯的吸收量达到70％.(2)唑菌酯及其代谢产物在黄瓜植株中的结合残留量随时间的增加而增加,而可提态残留呈现先上升后下降的趋势.(3)本研究共检测到黄瓜植株的7个放射性代谢产物,其中之一为中间态代谢产物.     

不同环境因子及施药量对土壤中唑菌酯残留的影响

在实验室条件下研究了土壤pH、温度、含水量及施药量对新型杀菌剂唑菌酯(E-2-(2-((3-(4-氯苯基)-1-甲基-1H-吡唑-5-基氧)甲基)苯基)-3-甲氧基丙烯酸甲酯)在土壤中残留量的影响。结果表明,在25d的培养时间内,随土壤含水量的增加,唑菌酯在土壤中的残留量减少;土壤含水量增加到60%田间最大持水量时,其残留达最低,为1.81μg/g,而在淹水环境中其残留量增加。随着土壤温度的升高,唑菌酯的残留呈现先降低后升高的趋势,4℃时的残留达最大(3.86μg/g)。土壤pH对其在土壤中的残留具有明显影响,在中性和弱碱性土壤中均具有相对较低的残留。在1～10μg/g施药量时,唑菌酯在土壤中的残留比例随其施药量的增加而少量降低,在药剂浓度为20μg/g时,土壤中唑菌酯的残留率为42.4%。     

PBDEs好氧微生物降解动力学过程及热力学机制研究

多溴联苯醚(PBDEs)是一种曾在全球范围内被广泛使用的溴代阻燃剂,具有半挥发性、生物蓄积性、神经毒性和内分泌干扰效应等,严重威胁生态环境和人体健康安全。本研究选择典型好氧降解菌伯克氏菌属LB400,对环境中普遍检出的中低溴联苯醚开展了降解动力学过程研究,探讨了外加碳源作为共代谢底物对降解性能的影响,模拟计算了降解中关键反应路径热力学状态函数性质变化,以揭示其与表观降解速率常数k之间的相关关系。结果表明:联苯作为共代谢底物时PBDEs的去除效率最高,在降解菌的作用下,0~120 h内中低溴代PBDEs均能够发生降解,降解过程符合一级反应动力学。羟基化反应可能是PBDEs微生物降解过程的速控步骤,相比于间/对位取代,活性氧自由基如·OH更倾向于攻击苯环碳原子的邻/间位置,这为揭示PBDEs好氧微生物降解的分子作用机制,促进土壤中高效好氧降解菌的选育与污染修复应用提供了科学依据。     

不同pH和氧气条件下土壤古菌与海洋古菌的竞争适应机制

pH和氧气是古菌氨氧化活性的关键限制因子。然而,复杂土壤中不同古菌生态型（土壤古菌和海洋古菌）对pH和氧气的竞争适应规律尚未有相关报道。选择活性氨氧化古菌（ammonia-oxidizing archaea, AOA）为类海洋古菌Group1.1a-associated的酸性森林土（ pH5.40）和活性氨氧化古菌为土壤类古菌Group 1.1b的碱性水稻土（ pH8.02）,调节混合土壤pH和氧气浓度;设置稳定性同位素核酸探针实验,通过微宇宙室内培养,监测土壤硝化强度;利用实时荧光定量qPCR和454高通量测序研究pH和氧气对土壤氨氧化古菌和细菌的影响规律。结果表明：pH3.8下没有硝化作用发生,而pH6.0和7.6则发生了强烈硝化作用,且高氧环境下硝化作用强于低氧环境;加底物培养后,氨氧化古菌数量明显增加;活性氨氧化古菌几乎全为土壤类古菌Group 1.1b。研究表明：尽管氧气对硝化作用也有一定影响,但pH是影响硝化作用的主要因素;与类海洋古菌相比,土壤类古菌Group?1.1b更能适应高氧和低氧的碱性土壤环境,因此具有更强的竞争力。     

高粱在不同氮源处理下分泌生物硝化抑制剂的差异

高粱根系能分泌抑制土壤亚硝化细菌的物质,称为生物硝化抑制剂.在铵态氮存在时,这类物质会大量分泌,而以硝态氮为氮源时则分泌很少.目前还不清楚,这是因为不同氮素代谢的差异所引起的,还是根系吸收铵态氮后根际酸化影响了硝化作用.因此本研究通过砂培试验,用铵硝营养处理高粱根系,并且控制pH,最后收集根系分泌物,利用一种荧光标记的亚硝酸细菌来测定高粱分泌的硝化抑制剂活性,计算其分泌速率.结果发现,铵态氮是导致根系大量分泌硝化抑制剂的主要原因,并且在根际pH＜6时,硝化抑制剂的活性与分泌速率随着根系分泌氢离子数量的增加而增强.研究表明,铵态氮营养下高粱根系分泌生物硝化抑制剂高于硝态氮营养可能是高粱根系保护根际铵氧化,提高氮素利用率的一个重要生理机制.     

中国东部太湖地区酸性水稻土团聚体上铜的专性和非专性吸附动力学研究

The Taihu Lake region in East China has become prone to soil acidification, which changes heavy metals such as copper(Cu) in soil into water-soluble species and increases the mobility and contamination risks of heavy metals in the biological environment. In this study, the kinetics of Cu2+sorption by the bulk soil and the aggregate size fractions of an acidic paddy soil collected from the Taihu Lake region, the effects of temperature on Cu2+sorption, and the p H changes of the solution were investigated by static sorption and magnetic stirring. The aggregate size fractions were prepared by low-energy ultrasonic dispersing and freeze-drying. The total sorption amounts of the bulk soil and the aggregate size fractions for Cu2+followed a descending order of clay > coarse sand > bulk soil > silt> sand, corresponding to those of organic matter content, free iron oxide content, free aluminum oxide content, and cation exchange capacity. The kinetic sorption curves of Cu2+by the bulk soil and the aggregates, which were divided into two stages(rapid and slow sequentially), were well fitted by the first-order equation, the diffusion equation, and the Elovich equation, showing significant correlations(P < 0.05). Specific and non-specific sorption dominated in the fast and slow stages, respectively, and the former was predominant throughout the sorption process. The specific sorption accelerated and the non-specific sorption decelerated with rising temperature. The p H of the solution decreased significantly during the specific sorption and remained unchanged or increased slightly during the non-specific sorption. When the specific sorption terminated, the p H of the solution was minimized nearly simultaneously.The sorption progress of Cu2+by the bulk soil significantly preceded that by the aggregates. Therefore, heavy metal contamination may be another factor reducing soil p H and metal sorption forms should be taken into consideration in studies of mitigating soil heavy metal pollution or determining environmental capacity of heavy metal in soil.     

土地利用方式对田间植物残体中C、N矿化的影响

Four kinds of plant materials(astragalus,azolla,rice straw and water hyacinth) were allowed to decom-pose for 10 years in two soils with different mineralogical characteristics in fields under upland and submerged conditions.Greater amounts of C and N from azolla were retained in soils throughout the 10-year experi-mental period compared to those from the other plant materials.The residual C of all the plant materials in the two soils under upland conditions mineralized at rates corresponding to half-lives between 4.4-6.6 years,while the corresponding figures for those under submerge conditions were between 6.5-13.1 years,Minera-liztion of residual organic N followed the same pattern as residual C.Compared to residual C,however,the mineralization rates of residual organic N in most cases were significantly lower and the percentages of added N retained in soils were higher.More N from plant materials was retained in the yellow-brown soil than in the red soil,but no consistent differences in the amounts of C from plant materials and in the mineraliztion rates of both residual C and residual organic N between the wto soils could be folund.     

An assessment of potential pesticide transmission,considering the combined impact of soil texture and pesticide properties: A meta-analysis

Pesticides are widely employed as a cost-effective means of reducing the impacts of undesirable plants and animals. The aim of this paper is to develop a risk ranking of transmission of key pesticides through soil to waterways, taking into account physico-chemical properties of the pesticides (soil half-life and water solubility), soil permeability, and the relationship between adsorption of pesticides and soil texture. This may be used as a screening tool for land managers, as it allows assessment of the potential transmission risks associated with the use of specified pesticides across a spectrum of soil textures. The twenty-eight pesticides examined were differentiated into three groups: herbicides, fungicides and insecticides. The highest risk of pesticide transmission through soils to waterways is associated with soils containing <20% clay or >45% sand. In a small number of cases, the resulting transmission risk is not influenced by soil texture alone. For example, for Phenmedipham, the transmission risk is higher for clay soils than for silt loam. The data generated in this paper may also be used in the identification of critical area sources, which have a high likelihood of pesticide transmission to waterways. Furthermore, they have the potential to be applied to GIS mapping, where the potential transmission risk values of the pesticides can be layered directly onto various soil textures.     

长期施肥对红壤pH、作物产量及氮、磷、钾养分吸收的影响*

在湖南祁阳典型红壤上进行不同施肥长期定位试验18年,观测了土壤pH、作物产量和氮、磷、钾养分吸收量的变化。结果表明,长期施用化学氮肥（单施氮肥、氮磷配施和氮磷钾配施）红壤pH明显下降,其中以单施氮肥降幅最大,18年降低了1.5个单位; pH降低主要发生在施肥的前8～10年,当pH下降到4.5时,其下降速度趋于缓慢并相对稳定。施用有机肥（化学肥料配施有机肥和单施有机肥）,土壤pH保持稳定或较试验开始有所升高,以单施有机肥处理pH升幅最大,升高1.0个单位。不施肥和施用化学氮肥的作物产量随着施肥年限均显著降低,其中小麦产量平均每年下降11～104 kg/hm2,玉米产量平均每年下降 24～210 kg/hm2; 而施用有机肥的作物产量保持稳定或稳定增加,其中化学肥料配施有机肥的玉米产量平均每年增加 101 kg/hm2。施用化学氮肥处理（除氮磷钾配施处理的玉米外）作物产量和氮、磷、钾养分吸收量与土壤pH均存在极显著正相关。可见,pH降低是作物产量和氮、磷、钾养分吸收降低的主要原因之一; 而施用有机肥能改善红壤酸度,尤其是化学肥料配施有机肥能获得持续高产,是红壤区的最佳施肥模式。     

钙试剂对干旱胁迫玉米脱落酸与木质部汁液pH的影响

试验研究钙试剂对干旱胁迫玉米脱落酸与木质部汁液pH的影响结果表明,EGTA、异博啶和三氟啦嗪处理均能提高玉米木质部汁液pH;EGTA、异博啶处理后玉米叶茎根中脱落酸含量降低,木质部汁液中脱落酸浓度与叶茎根脱落酸含量并没有明显相关性,表现出复杂变化;三氟啦嗪处理后玉米根中脱落酸含量升高,茎、叶中脱落酸含量降低,且叶木质部汁液中脱落酸浓度亦降低,而茎、根木质部汁液中脱落酸浓度无明显变化。     

碳酸钙和锌对五种基因型小麦生长、锌吸收及营养液中HCO3-含量和pH的影响

以霍格兰营养液为介质,在不同的Zn(0、0.016、0.082.mg/L)与CaCO3(0、10、306、0.mg/L)用量下,将5种基因型冬小麦进行营养液混合培养,探讨Zn与CaCO3用量对小麦幼苗生长、Zn吸收及营养液中HCO3-含量和pH的影响。结果表明,5种基因型冬小麦中,S02-8、远丰998为缺锌敏感型,西杂1号为缺锌非敏感型,适量供Zn比高量供Zn更有利于小麦生长。低量CaCO3可在一定程度上促进小麦幼苗生长,而高量CaCO3会抑制生长;缺锌敏感型的生长量显著低于非敏感型,且前者的根冠比小于后者。加入CaCO3后对各基因型小麦Zn吸收量无显著影响,但随着供Zn量的增加,根系与地上部吸Zn量也随之增加,且高量供Zn时Zn在根部大量累积;缺锌敏感型小麦比非敏感型更易于在根系中累积Zn,而Zn向地上部的转移率远比非敏感型低。与不添加CaCO3相比,加入一定量CaCO3后,营养液中HCO3-浓度与pH值均有较大幅度上升,并且二者均随着CaCO3加入量增加而升高。在每10.d更换一次营养液的培养过程中,营养液pH值在一日内的波动范围在0.2个pH值单位内,但pH值总体上随着培养天数推移而呈上升趋势,10.d内上升范围在0.79～2.37个pH值单位;每10.d为一阶段的培养结束后,不同CaCO3用量间的pH值差异与开始时相比均大大减小。此外,因高量CaCO3抑制小麦幼苗生长,加剧缺Zn症状,但又不降低Zn吸收量,据此推测,高量CaCO3可能通过产生较高浓度的HCO3-而降低植物体内所吸收的Zn的生理活性。     

过碳酰胺在不同酸碱性土壤上的氨挥发特性研究

过碳酰胺是一种新型精细化工品，也是一种新型氮肥，在国外已得到广泛的应用和开发，而我国对其开发和应用刚刚起步。试验研究了3种酸性土壤和3种碱性土壤施入过碳酰胺（和尿素对照）后的氨挥发特性。结果表明，过碳酰胺和尿素在供试6种土壤上的氨挥发强度具有相同的规律，都是先从小到大出现峰值，然后又降低；3种酸性土壤氨挥发高峰期约在第7d左右，3种碱性土壤的氨挥发高峰期约在第3d左右。土壤氨挥发含量的变化与pH变化同步。在最初挥发高峰期阶段，过碳酰胺的氨挥发强度在6种土壤上都大于尿素，但在供试的3种酸性土壤上，过碳酰胺的氨挥发总量均略小于尿素，而在供试的3种碱性土壤上，却正好相反。