弗罗里硅土净化和凝胶色谱净化在土壤苯并(a)芘测定中的应用

采用ASE萃取-弗罗里硅土净化-HPLC法和ASE萃取-GPC净化-HPLC法测定土壤中苯并(a)芘,并将2种方法的测定结果作比对。试验表明,方法在0.02 mg/L~0.500 mg/L之间线性良好,当取样量为10 g时,弗罗里硅土净化土壤样品方法检出限为8.93×10~(-5)mg/kg,平均加标回收率为72.7%~73.8%,3次测定结果的RSD为4.0%~4.5%;凝胶色谱净化土壤样品方法检出限为1.98×10~(-5)mg/kg,平均加标回收率为88.8%~90.2%,3次测定结果的RSD为2.1%~2.8%。     

快速溶剂萃取-气相色谱/串联质谱法测定农作物中的有机氯农药

建立快速溶剂萃取,固相萃取柱净化,气相色谱/串联四极杆质谱检测分析农作物中23种有机氯农药残留的方法。以油菜为样品,加标浓度为5、10、25、50μg/kg时,平均回收率在72%~101%之间,相对标准偏差3%~14%(n=5)。8种农作物(莴笋、黄瓜、蒜苗、辣椒、油菜、茄子、玉米和水稻)加标浓度为25μg/kg时的平均回收率在71%~113%之间,相对标准偏差3%~16%(n=5)。方法检出限0.75~1.76μg/kg之间。     

固相萃取-高效液相色谱法测定废水中的酚类化合物

建立了Supelclean ENVI-Chrom P柱固相萃取-高效液相色谱法测定废水中11种酚类化合物的分析方法,并对固相萃取条件和液相色谱条件进行了讨论。该方法分离效果良好,净化效果明显,方法检出限为2×10-3~2×10-2mg/L,平行分析(n=6)的RSD为2.7%~16.4%,废水加标回收率除2,4-二硝基酚偏低以外,其他化合物的回收率为61.4%~115.8%。     

气相色谱法同时测定稻田中稻瘟酰胺和咪鲜胺残留

采用二氯甲烷萃取稻田水样品,土壤样品用丙酮-二氯甲烷(体积比为9∶1)混合溶液提取,二氯甲烷萃取,水稻植株样品用乙腈-二氯甲烷(体积比为9∶1)混合溶液直接萃取,用气相色谱法同时测定样品中稻瘟酰胺和咪鲜胺残留。该方法在0.012 2 mg/L~2.68 mg/L范围内线性良好,稻田土壤、田水、水稻植株中稻瘟酰胺的检出限分别为2.75μg/kg、1.83μg/L、3.80μg/kg,咪鲜胺的检出限分别为3.55μg/kg、2.66μg/L、5.62μg/kg。空白稻田土壤、稻田水和水稻植株样品3个浓度水平的加标回收率为80.3%~104%,RSD为3.0%~13.2%。     

离子色谱紫外检测法同时测定水中5种氯酚类化合物

建立了同时测定水中5种氯酚类化合物的离子色谱紫外检测法。水样经0.45μm水相针式滤器过滤后,以250 nm为检测波长,5%的氨水甲醇-1%的硫酸铵溶液(V∶V=80∶20)为流动相进行检测。结果表明,在2-氯酚质量浓度为0.1~1.6 mg/L,其余4种氯酚质量浓度为0.01~0.16 mg/L范围内,线性相关系数均>0.999;2-氯酚和2,4-二氯酚的检出限分别为0.03和0.004 mg/L,其余3种氯酚的检出限为0.003 mg/L。低、中、高3种加标浓度样品的加标回收率为94.1%~100.8%,相对标准偏差(RSD)为2.5%~9.9%。该方法前处理简单,灵敏度、准确度和精密度均较好,适用于基层检测机构对生活饮用水中5种氯酚类化合物的日常快速检测。     

超声浸取-离子选择电极法测定土壤中水溶性氟

采用水平震荡和超声浸取2种方法进行预处理,离子选择电极法测定土壤中水溶性氟化物。结果显示:土壤中水溶性氟化物的最佳预处理条件为纯水与土壤按10∶1混合,常温35 k Hz超声浸取30 min。超声浸取-离子选择电极法测定土壤中水溶性氟化物具有较好的精密度和准确性,此法在5.00~500μg范围内线性良好,检出限为0.5 mg/kg。对实际样品进行分析,氟的加标回收率为82.0%~110%,相对标准偏差为2.8%~6.4%(n=6)。对土壤有证标准物质进行分析,相对标准偏差为2.9%~4.6%(n=6),相对误差为-3.9%~2.7%。     

加速溶剂萃取-液相色谱测定土壤中酞酸酯类化合物

建立了加速溶剂萃取-液相色谱法测定土壤中14种酞酸酯类化合物的方法。结果表明,该方法对14种酞酸酯分离度较好,加标回收率为67.1%~128%,精密度RSD(n=6)为5.2%~15.0%,方法检出限为0.021~0.034 mg/kg。该方法操作简便、准确,具有较好的实用性。     

加压流体萃取-气相色谱质谱法测定土壤和沉积物中27种拟除虫菊酯类农药

建立了加压流体萃取-气相色谱质谱法测定土壤和沉积物中27种拟除虫菊酯类农药的方法。以丙酮/正己烷(V∶V=1∶1)为萃取溶剂,在120℃和10. 3 MPa条件下静态萃取7 min,循环3次,石墨化炭黑串接氨丙基键合硅胶固相萃取柱净化,HP-5MS UI色谱柱分离,优化了提取和分析过程的重要条件。方法检出限为0. 001~0. 012 mg/kg,土壤中低、高浓度的加标回收率范围分别为68. 3%~123%和75. 3%~115%,沉积物中低、高浓度的加标回收率范围分别为67. 1%~120%和78. 6%~110%,单一目标物的相对标准偏差(RSD)均<20%(n=6)。实验结果表明,该方法消耗溶剂少、效率高、检出限低、精密度和准确度好,适用于土壤和沉积物中拟除虫菊酯类农药残留的测定。     

固定污染源中苯系物的便携式气质联用检测方法研究

建立了适用于固定污染源气体中苯系物的日常检测和监督性检测的便携式气质联用分析方法。利用Mars-400便携式GC-MS具有定量环和吸附管同时并存的功能,无需更换仪器部件,根据预测浓度,选择相应的进样模式(10mg/m3为浓度切换点),以保留时间和特征离子定性,总离子峰面积定量,现场对固定污染源中高低浓度苯系物进行直接分析。在吸附管和定量环两种模式下,选择苯系物的质量浓度范围分别为0.1~10 mg/m3、5~100 mg/m3,两者的线性相关系数均≥0.993,相对标准偏差(n=7)为5%~14%,方法回收率在84%~112%之间。     

毛细管柱气相色谱法测定空气中二硫化碳

利用毛细管柱对二硫化碳进行分离,火焰光度检测器(FPD)进行检测,建立了空气中二硫化碳的毛细管柱气相色谱测定法。该方法检出限为0.03 mg/m~3,空白样品加标回收率为91.3%~102.8%,精密度(RSD,n=7)为1.04%~3.91%,变异系数为1.00%~3.93%。实验结果表明,该方法准确可靠、灵敏度好、分析速度快、操作简便,适用于空气中二硫化碳的测定。     

高氯酸铁可见分光光度法测定水中叠氮化物研究

基于Fe~(3+)显色技术,建立了测定地表水、地下水、生活污水和工业废水中叠氮化物的高氯酸铁分光光度法。研究结果表明:N_3~-与Fe~(3+)反应生成的棕红色络合物的特征吸收峰为454 nm;氨基磺酸铵可有效掩蔽NO_2~-的干扰,蒸馏能消除色度、CN~-、SCN~-硫化物等对测定的影响;当取样体积为150 mL、蒸馏定容体积为100 mL、使用10 mm比色皿时,方法检出限为0.08 mg/L(以N_3~-计),测定下限为0.32 mg/L;平均回收率为88.0%~104%,相对标准偏差(n=6)为0.3%～5.6%。对实际工业废水样品进行了测定,结果为1.37 mg/L。该方法准确度高、精密度好、操作简单,能够满足水污染物排放标准中叠氮化物的测定要求。     

三峡水库干流氮和磷含量的季节变化

三峡水库成库后对6个水平断面、4个垂直断面采样分析,对水体水质参数、不同化学形态N以及不同物理形态P的水平分布和垂直分布进行了研究。研究结果表明,成库后TP、NH3-N、NO2--N、NO3--N、IN含量范围分别在0.06～0.34、0.01～0.72、0.002～0.100、0.76～2.09、0.855～2.52 mg/L。TP分布为丰水期>平水期>枯水期,受悬浮物沉降的影响,TP在水库区域含量低于上游区。枯水期、平水期水体中TP以可溶解态为主,丰水期以颗粒态为主。NO2--N、NO3--N、IN含量均为平水期>枯水期>丰水期。水体中IN以NO3--N为主,占IN70%～90%。NO2--N比例最低,占IN3.5%以下。表明水体虽受成库影响流速减缓,但水体依然有较强的自净能力。垂直分布上,TP、IN在3个层次变化不显著,未出现分层现象。各采样站点TP、NO3--N、IN通量和流量有显著相关。     

Monitoring the impact of dissolved oxygen and nitrite on anoxic biofilm in continuous denitrification process

An anoxic biofilm involved in continuous denitrificationprocess was monitored to investigate the effect of differentconcentrations of influent dissolved oxygen (DO) or nitrite onthe biofilm. Microelectrode measurements evidenced nitrateremoval activity of biofilm. When different concentrations ofDO were applied to the reactor, generally decreasedconcentrations of DO were observed as bed depth increased fromthe bottom of the reactor. Greatest decrease of the DO wasobserved in the lower 20% of the bed depth. Nitrate removalefficiency was inversely proportional to influent DOconcentrations (8.3-11.9 DO mg L^-1) or nitrite loadingrates (0-5.5 N-NO₂ ^- kg m^-3 day^-1) employed in this study. Nitrite loading rates to achieve morethan 90% of nitrate removal efficiency were 1.46 N-NO₂ ^-kg m^-3 day^-1 or less at pH 7.5 and 0.34 N-NO₂ ^- kg m^-3 day^-1 or less at pH 6.8. Nitrate removal efficiency was 63% or more within the lower 20% of the bed depth at the nitrite loading rates that allowed more than 90% of nitrate removal efficiency of the reactor. The results of this study provide first quantitative data that nitrate removalperformance of an anoxic biofilm is inhibited by DO or nitrite,reported to be a limiting factor in the suspended biologicaldenitrification process.     

Inorganic Ion Levels of Soils and Streams in some Areas of Ogoniland, Nigeria as Affected by Crude Oil Spillage

The inorganic ion concentrations of soils and streams in the three locations (Yorla, Zaakpon and Goi) in Ogoniland,Nigeria affected by crude oil spillage were investigated. In general, inorganic ion concentrations of polluted soilsand streams varied significantly (p = 0.05) from those of unpolluted soils and streams. Anions such as nitrate (NO ₃ ^- ), sulphate (SO ₄ ^2- ) and chloride(Cl^-) showed significantly (p = 0.05) higher values inthe polluted soils and steams than in the unpolluted controls. The phosphate (PO ₄ ^3- ) values were lowerin the polluted soils and streams than in the unpolluted controls.PO ₄ ^3- , NO ₃ ^- , SO ₄ ^2- and Cl^- concentrations were generally significantly (p = 0.05) higher in soils and streams from Yorla, Zaakpon and their control than in Goi North, Goi South and Goi control.Exchangeable cations and trace metal concentrations weresignificantly (p = 0.05) higher in the polluted soils andstreams than in the unpolluted controls. Yorla and Zaakponpolluted soils and streams had higher concentrations of theexchangeable cations and trace metals compared to valuesfrom Goi, except for Na. Results also showed significantlyhigher values of heavy metals (Pb, Cd, Cr and Ni) in the polluted soils compared to their controls, and values werealso significantly (p = 0.05) higher in Yorla, Zaakpon andtheir control compared to Goi North, Goi South and Goicontrol. Values obtained in polluted streams were higherthan in the unpolluted though not significant at the 5%level (p = 0.05). The anionic and cationic concentrationsof Yorla and Zaakpon soils and streams were generally higherthan those of Goi, indicating that Yorla and Zaakpon areaswere more polluted than Goi.Although the concentrations of most of the anions andcations analysed in the polluted soils and streams werewithin the World Health Organisation's permissible valuesfor the protection of humans and environment, the streams ofYorla, Zaakpon and Goi are in general being polluted withinorganic ions. This may make these soils and streamsunacceptable for domestic and industrial uses if not treated,and soils (farmlands) may also become unsuitable for agricultural purposes.     

Spatial and seasonal distribution of nitrogen in marsh soils of a typical floodplain wetland in Northeast China

Horizontal and profile distributions of nitrogen in marsh soils in different seasons were studied in a typical site within the Erbaifangzi wetland in Northeast China. Results showed that there was higher spatial heterogeneity for nitrate nitrogen (NO₃^--_{3}^{-}-N) and ammonium nitrogen (NH₄⁺_{4}^{+}–N), as well as available nitrogen (AN), in surface soils in July compared to that in September. Relative to July, the mean nitrogen contents in surface soils were slightly higher in September; however, in November, soils contained significantly lower NO₃^--_{3}^{-}-N and NH₄⁺_{4}^{+}–N, higher AN, organic nitrogen (Org-N), and total nitrogen (TN). Except for mineral nitrogen, no significant differences were observed between Org-N and TN contents in September and November. Nitrogen contents generally declined exponentially with depth along soil profiles in three sampling dates (July, September, and November), except for a significant accumulation peak of NO₃^--_{3}^{-}-N at the 20–30 cm depth in September. However, NH₄⁺_{4}^{+}–N contents showed a vertical alternation of “increasing and decreasing” in both July and September, while nearly kept constant with depth in November. The depth ranking of nitrogen showed the shallowest distribution for AN, followed by Org-N and TN, while deeper distributions for NO₃^--_{3}^{-}-N and NH₄⁺_{4}^{+}–N. TN, Org-N, and AN were significantly correlated with soil organic matter and total phosphorus. Soil pH values were significantly correlated with TN and AN contents in surface soils. Clay contents showed significant correlations with nitrogen contents except for NO₃^--_{3}^{-}-N in surface soils and NH₄⁺_{4}^{+}–N in profile soils. However, soil moisture was not significantly correlated with nitrogen contents among all soil samples.     

Dissipation and residue of 2,4-<Emphasis Type="SmallCaps">d</Emphasis> in citrus under field condition

The dissipation, residues, and risks of 2,4-dicholrophenoxyacetic acid (2,4-d) in citrus under field condition were investigated based on a simple ultra-performance LC (UPLC)-MS/MS method. The results indicated that the residue level of 2,4-d in citrus did not degrade gradually with sampling time under field condition. At pre-harvest intervals (PHI) of 20–40 days, 2,4-d residues were 0.021–0.269 mg/kg in citrus flesh, 0.028–0.337 mg/kg in whole citrus, and 0.028–0.376 mg/kg in citrus peel, all bellow the China maximum residue limit in citrus (1 mg/kg). Risks of 2,4-d were assessed by calculation of risk quotient, and the results revealed no significant health risks after consumption of citrus.     

湿法脱硫烟气中多形态颗粒物的测量方法及组分特征

为全面测量固定源湿法脱硫烟气中多形态颗粒物的排放浓度及其离子组成特征,提出了一种基于一级冷凝、二级过滤和一级冲击吸收的多形态烟气颗粒物的同步测量方法,外场实测了3种湿法脱硫和除尘工艺的排放水平。现场测试表明：简易湿法除尘脱硫（NaOH法）一体化装置烟气中可过滤颗粒物（FPM）浓度为（36±11）mg/m³,可逃逸颗粒物（EPM）浓度为（33±7）mg/m³;氧化镁法+布袋除尘工艺烟气中FPM浓度为（14±5）mg/m³,EPM浓度为（13±6）mg/m³;石灰石-石膏脱硫+电袋除尘工艺烟气中FPM浓度低,小于3 mg/m³,EPM浓度为（6±1）mg/m³;烟气中EPM是传统滤膜法检测FPM浓度的0.7~5.7倍,EPM的主要存在形态为冷凝液中的可溶解颗粒物（DPM）,颗粒物的组分与脱硫方法密切相关,各形态颗粒物的主要组分是SO₄^2-、SO₃^2-、NO₃^-、NO₂^-、NH₄⁺、Cl^-、Na⁺、Mg²⁺和Ca²⁺等离子。     

气相色谱法测定工业废气中的异丙醇

用活性炭吸附管采集吸附工业废气中的异丙醇,经二硫化碳解析后由自动进样器送入气相色谱仪中分离并由FID检测器检测。2 mL二硫化碳解吸溶剂中异丙醇的绝对量为1.57~6.28 mg时,测定结果的相对标准偏差为2.4%~7.6%(n=5);当样品采集量为10 L时,方法检出限为0.3 mg/m³。所用活性炭采样管对异丙醇的吸附效果良好,100 mg活性炭对异丙醇的穿透容量大于15 mg;二硫化碳溶剂对吸附在活性炭中的异丙醇解吸效果较好,异丙醇加标量为3.92~15.70 mg时,解吸效率为93.9%~100.5%。     

Evaluating the Applicability of Regulatory Leaching Tests for Assessing Lead Leachability in Contaminated Shooting Range Soils

The toxicity characteristic leaching procedure (TCLP) is the current US-EPA standard protocol to evaluate metal leachability in wastes and contaminated soils. However, application of TCLP to assess lead (Pb) leachability from contaminated shooting range soils may be questionable. This study determined Pb leachability in the range soils using TCLP and another US-EPA regulatory leaching method, synthetic precipitation leaching procedure (SPLP). Possible mechanisms that are responsible for Pb leaching in each leaching protocol were elucidated via X-ray diffraction (XRD). Soil samples were collected from the backstop berms at four shooting ranges, with Pb concentrations ranging from 5,000 to 60,600 mg kg⁻¹ soil. Lead concentrations in the TCLP leachates were from 3 to 350 mg l⁻¹, with all but one soil exceeding the USEPA non-hazardous waste disposal limit of 5 mg l⁻¹. However, continued dissolution of metallic Pb particles from spent Pb bullets and its re-precipitation as cerussite (PbCO₃) prevented the TCLP extraction from reaching equilibrium at the end of the standard leaching period (18 h). Thus, the standard one-point TCLP test would either over- or under-estimate Pb leachability in shooting range soils. Lead concentration in the SPLP leachates ranged from 0.021 to 2.6 mg l⁻¹, with all soils above the USEPA regulatory limit of 0.015 mg l⁻¹. In contrast to TCLP, SPLP leaching had reached equilibrium, with regard to both pH and Pb concentrations, within the standard 18 h leaching period, and the analytical SPLP results were in good agreement with those derived from modeling. Thus, we concluded that SPLP is a more appropriate alternative than TCLP for assessing lead leachability in range soils.     

北京夏季大气主要含氮无机化合物的变化规律与相互作用

利用SJAC-MOBIC/FIA在2006年8月16日—9月9日在线测量了北京城市大气细颗粒物中主要水溶性含氮离子组分(NO₃^-和 NH₄⁺),与重要含氮气态污染物(HNO₃、HNO₂和 NH₃),以追踪细颗粒物中含氮二次无机组分和含氮气态污染物的变化规律及其相互作用。观测期间,NO₃^- 和 NH₄⁺的平均浓度分别为13.08和11.93 μg/m³,它们与SO₄^2-浓度之和在细颗粒物(PM_2.5)中的平均比例为55%,明显高于其他季节;污染过程中,积聚模态颗粒物体积浓度及其与爱根核模态颗粒物体积浓度比值逐渐增加,说明二次转化是北京夏季细颗粒物的重要来源。白天HONO迅速光解产生OH自由基,而OH自由基是生成HNO₃的重要物种,因此HONO和HNO₃具有相反的日变化规律。在温度较高的白天,大气环境不利于NH₄NO₃的生成与存在;夜间低温高湿的条件下硝酸铵理论平衡系数Ke与气态氨和硝酸的乘积Km相当或低于后者,较有利于NH₄NO₃的生成。北京夏季大气具有足量气态NH₃以中和硫酸盐;但在NO₃^-与阳离子的电荷平衡中,金属阳离子也非常重要。