自动电位滴定仪应用于地下水六项指标的连续滴定

地下水中六项指标(pH、总碱度、氯离子、钙离子、镁离子及硫酸根)的分析需要对每个指标单独进行取样检测,步骤繁琐且效率较低。同时总碱度、氯离子、钙离子、镁离子及硫酸根通常采用手动目视滴定,检测结果存在人为操作误差,精密度和准确度相对较差。本文建立了准确快速测定地下水中六项指标的分析方法,只需2次取样,采用自动电位滴定仪自动判定终点,加液器可精确控制标准溶液加入量至0. 1μL,并且通过调整检测顺序、溶液酸度和加入掩蔽剂的方法消除相互干扰。本方法的加标回收率为93. 5%～120. 0%,相对标准偏差(RSD,n=10)为0. 18%～11. 33%。电位滴定法得到的数据相比标准方法的平行性更好,尤其是当所测定水样较为浑浊或者有颜色时测定数据更稳定。     

基于灰色关联度的地下水化学成分分析

依据新疆某水库周边耕地地下水水样化验数据,应用灰色关联分析与相关分析相结合的方法,分析了地下水主要成分与总硬度、总碱度、电导率及矿化度4个指标之间的关系.结果表明,总硬度变化主要受Ca2+影响,水中HCO3-含量与总碱度关系密切,电导率主要受Mg2+影响,Na+、K+和与Mg2+对矿化度有较大影响.通过相关分析,发现它们之间相关性极为显著.     

自动电位滴定仪应用于测定海洋沉积物中有机碳的可行性研究

自动电位滴定仪具有操作简便、测定速度快的优势,减少了人为操作的影响,本文使用自动电位滴定仪测定海洋沉积物中有机碳的含量,并与国家标准(GB 17378.5—2007)中根据滴定过程中溶液颜色变化用肉眼判定滴定终点的方法进行了对比分析,确定通过仪器自动判断滴定终点实现准确测定的可行性。结果表明:自动电位滴定的方法检出限为0.029%,人工肉眼判定终点的方法检出限为0.086%,在滴定终点判定方面两种方法无显著性差异,但自动电位滴定仪的准确度和精密度更优,在一定程度上可代替肉眼判定滴定终点。实际应用过程中也发现,当滴定的溶液体系由于氧化还原反应、络合作用等影响因素使电位变化较为复杂时,自动电位滴定仪有可能会得到多个等当点而无法判断哪个等当点是真正的目标等当点,此时需要利用肉眼进行辅助确定。     

马氏距离判别模型在矿井突水水源判别中应用

根据某矿井水质资料,建立了该矿判别突水水源的数学模型,利用VB程序开发了马氏距离判别软件。选择了K＋、Na＋、Ca2＋、Mg2＋、HCO3-、SO42-、总硬度、碱度、pH、矿化度11项指标作为评价因子,选取20个典型水样作为距离判别方法的训练样本,获得了判别模型,并用样本数据的回判处理进行验证。应用该模型对6个待测水样进行判别,并与Fisher判别结果进行比较,结果表明：其结果与实际情况吻合较好。     

酸碱滴定中指示剂对滴定分析准确度的影响

在酸碱中和标定中采用甲基橙做指示剂,滴定终点难以准确判断。用甲基红-溴甲酚绿混合指示剂代替甲基橙指示剂,测定终点溶液颜色由绿色变为酒红色,颜色反差强烈,肉眼识别敏锐,实验结果的相对平均偏差小于3%,滴定误差小,结果满意。选择不同指示剂及其不同用量指示剂在酸碱反应中对滴定误差的影响也不同。     

EDTA容量法连续测定钙和镁的改进

改进了用EDTA连续快速测定矿石中钙和镁的方法。在用EDTA滴定钙之后的溶液中加入NH4Cl，使溶液中的碱度降低至pH10左右，以Mg(OH)2沉淀溶解为标志，加入pH10的缓冲溶液，补加K－B指示剂，用同一EDTA标准溶液继续滴定镁。此法克服了用HCl调节pH值法滴定镁结果系统偏高的缺点，经大量生产考察，结果准确，稳定，与分别滴定后从钙镁合量差减法和外检结果十分一臻，对ω（MgO)为21.10%的样品进行精密度试验，其RSD（n=10)为0.6%。     

2-（5-氯-2-吡啶偶氮）-5-二乙基氨基酚作络合滴定指示剂测定锌

对2-（5-氯-2-吡啶偶氨）-5-二乙基氨基酚（5-Cl-DEPAP）作锌的络合滴定指示剂进行了实验。在pH5．5的HAc—NaAc介质中，以5-Cl-DEPAP作指示剂，EDTA标准溶液滴定锌，溶液颜色由紫红色变为亮黄色，终点变化敏锐，易于观察，锌量在0-25mg与EDTA消耗量成正比。方法用于化学试剂和铝合金中锌的测定，5次测定的RSD小于0．1％。结果表明，5-Cl-DEPAP符合络合滴定对指示剂的基本要求，扩大了该试剂的应用范围。     

铁、铝的快速直接络合滴定

铁、铝是经常需要分析的项目,常量铁、铝的分析方法很多,在众多的分析铁的容量分析方法中,目前主要采用氧化—还原法,而其中又以采用经典的重铬酸钾容量法为主。但此法最大的缺点是要用剧毒的升汞和致癌的六价铬,易造成环境污染。所以近几年来,广大分析工作者,为了改进铁的分析方法,曾进行了大量的研究,无汞盐分析铁的文章大量涌现,但至今仍无重大突破和进展。络合滴定法测定铁不使用剧毒的升汞,也不使用致癌的六价铬,但由于缺乏适合的指示剂至今仍未能广泛使用。现在主要是采用磺基水杨酸作指示剂,但它与铁生成的颜色很弱,近等当点时颜色变化缓慢。而且当铁的含量高时,铁与乙二胺四乙酸二钠所形成的络合物的颜色和铁与磺基水扬酸所形成的络合物的颜色均为相似的黄色,难以判断滴定的终点,所以在对铁的络合滴定中,主要是寻找优良的指示剂。广大分析工作者进行了大量的研究,所建议的指示剂中各有优劣,仍未能找到能同时兼作铁、铝络合滴定时的优良指示剂。铝的分析目前主要是采用二甲酚橙作指示剂的络合滴定法,用氟盐取代后再用金属盐反滴定。分析手续繁杂,需两次煮沸并冷却,费时较长,当有钛存在时,在大多数情况下,得到的结果还是铝,钛合量,需再单独分析钛后用差减法求得铝的含量,而在络合滴定过程中与铝共存于溶液中的钛往往还不是定量络合;因而造成铝的分析结果不正确。基于以上情况,本研究工作的目的是寻找一种同时兼作铁,铝络合滴定的优良指示剂,建立一个简便、快速、经济,不污染环境的连续直接络合滴定铁、铝的新方法。     

粗铜中铜含量测定方法的改进

笔者将《粗铜化学分析方法第1部分:铜量的测定碘量法》(YS/T 521.1-2009)中滴定管改用校准大度移液管与酸式滴定管进行滴定,这样易掌控终点颜色变化。对电解铜片标样平行测定12份,相对标准偏差RSD为0.046%,相对误差RE为-0.070%,其测定值与参考值基本相符。     

对煤灰成份分析中测定铁、铝含量的改进

煤灰成份分析中测定铁、铝含量的现行方法没考虑煤灰成份中含有铜、锌、铅等成份会造成测试误差的特殊情况,而且操作都是热滴定(80℃),待测组分含量不同使滴定终点的颜色不同,容易造成主观误差,是本方法的不足之处。     

Determination of the Concentration of Carbonic Species in Natural Waters: Results from a World‐Wide Proficiency Test

The results of an international interlaboratory proficiency test for the determination of carbonic species are presented. Eight laboratories analysed twelve water samples (four synthetic waters, one lake water, four geothermal waters, one seawater and two petroleum waters) by two methods: (a) individual laboratory analytical procedure and (b) acid–base titration curves in tabular form following a standardised protocol. In case (b), the concentrations of carbonic species were calculated by the organiser using the (1) Hydrologists' method, (2) Geochemists' method and/or (3) initial pH and total alkalinity method. For synthetic waters, the averaged % trueness and precision of measurement of the two methods were (trueness = 7.6, precision = 9.4) and (9.0, 3.4) for total alkalinity, and (6.6, 31.0) and (7.8, 6.1) for carbonic alkalinity, respectively. This indicates that the total alkalinity calculation procedure is in general correct in the individual laboratory method, but the carbonic alkalinity calculation procedure has serious problems. The measurements of total alkalinity for lake and seawaters were in agreement in both the methods; however, the individual laboratory measurement method for geothermal and petroleum waters was conceptually incorrect. Thus, the analytical procedures for the determination of carbonic species were reviewed. To apply the Hydrologists' and/or Geochemists' methods, the location of NaHCO₃EP and H₂CO₃EP is necessary, even for samples with pH lower than that of NaHCO₃EP, and a backward titration curve after complete removal of CO₂ must be performed. The initial pH and total alkalinity method is appropriate where a complete analysis of species that contribute to the alkalinity is known.     

Combined effects of water pH and alkalinity on the accumulation of lead, cadmium and chromium to Labeo rohita (Hamilton)

Influence of pH (5.5, 7.0 and 8.5) and alkalinity (40 to 200 mg/L as CaCO₃) on the accumulation of Pb (NO₃)₂ CdCl₂, H₂O and K₂Cr₂O₇ to Labeo rohita (Hamilton) was investigated in the laboratory. Highest accumulation of Pb and Cr in whole fish occurred at pH 5.5 and at alkalinity level of 40 to 46 mg/L as CaCO₃ compared to 7.0 and 8.5. In case of Cd maximum accumulation occurred at pH 7.0 and at alkalinity of 100 mg/L as CaCO₃ than that of pH 5.5 and 8.5 and alkalinity 42 and 156 mg/L as CaCO₃. Maximum accumulation of lead and chromium occurred at total alkalinity level of 40 and 46 mg/L as CaCO₃, respectively while maximum accumulation of cadmium occurred at an alkalinity level of 200 mg/L as CaCO₃. A significant (p<0.05) linear relationship was demonstrated between increasing pH/ alkalinity and decreasing accumulation in Pb and Cr treatment at all exposure period while for Cd there was no significant linear relationship established.     

Water quality index and fractal dimension analysis of water parameters

Statistical analysis of water quality parameters were analyzed at Harike Lake on the confluence of Beas and Sutlej rivers of Punjab (India). Mean, median, mode, standard deviation, kurtosis, skewness, coefficient of variation, regression lines, correlation coefficient, Hurst exponent, fractal dimension and predictability index were estimated for each water parameter. Monthly variation of water quality index using month-wise and parameter-wise value of quality rating and actual value present in water sample was calculated and compared with World Health Organization/Environmental Protection Agency standard value of these parameters. It was observed that Brownian time series behavior exists of potential of hydrogen with total dissolved solids, hardness, alkalinity, sulfate, chloride and conductance parameters; biochemical oxygen demand with total dissolved solids, hardness, alkalinity, sulfate, chloride, conductance and calcium parameters; dissolved oxygen with total dissolved solids, hardness, alkalinity, sulfate, chloride, conductance and calcium parameters; ferrous with total dissolved solids, hardness, alkalinity, sulfate, conductance and calcium parameters; chromium with total dissolved solids, hardness, alkalinity, sulfate, chloride, conductance and zinc parameters; zinc with total dissolved solids, hardness, sulfate, chloride, conductance and calcium parameters; fluoride with total dissolved solids, hardness, alkalinity, sulfate, chloride and conductance parameters; nitrate with total dissolved solids, sulfate and conductance parameters; nitrite with potential of hydrogen, total dissolved solids, hardness, alkalinity, sulfate, chloride, conductance and calcium parameters. Also, using water quality index, it was observed that water of the lake was severely contaminated and became unfit for drinking and industrial use.     

Alkalinity production as an indicator of failure in steel slag leach beds treating acid mine drainage

Acid mine drainage is a serious environmental problem throughout mining regions of the US and around the world. In Appalachia, reuse of steel slag from steel production as a source of alkalinity for treatment of acid mine drainage has become a common practice. In these systems, dubbed steel slag leach beds, relatively clean surface water is percolated through a bed of steel slag to add large amounts of alkalinity to the water before mixing it with acidic, metalliferous mine water. These beds do not operate consistently and their failure mechanisms are poorly understood. Using the experience of Raccoon Creek watershed in southern Ohio, the alkalinity distribution of the discharge of six steel slag leach beds is compared. Two of these beds are still functional, one has been abandoned and three are operating poorly. The difference in alkalinity distribution between these beds suggests that a carbonate-dominated alkalinity system is an indicator of a poorly performing steel slag leach bed, while a more even distribution between hydroxide, carbonate and bicarbonate may point to more ideal operating conditions. In eight laboratory column experiments, this evidence was then expanded upon by testing different mixed media substrates (differing mixes of steel slag, wood chips and river gravel) to see which provided the most ideal alkalinity distributions. The columns that had steel slag mixed either with wood chips or wood chips and river gravel outperformed the column with slag only in terms of alkalinity distribution, perhaps due to microbial processes or increased hydraulic conductivity without significant added calcium or carbon that could drive calcium carbonate precipitation within the beds and causing them to fail.     

岩浆岩相对碱度的意义和算法

本文从酸碱电子理论出发,提出了一种新的岩浆岩碱度参数——相对碱度及其计算方法。岩石或矿物的相对碱度是其中的氧元素丢失电子能力的综合度量。规定硅作为其他阳离子对氧原子屏蔽作用的比较基准,用各金属氧化物与二氧化硅的反应焓变值作为它们相对于二氧化硅对矿物或岩石相对碱度的贡献。综合各氧化物的碱度贡献使得到岩石或矿物的相对碱度值。计算表明,主要造岩标准矿物和各种岩浆岩的相对碱度值顺序与传统用法基本一致。     

Short chain aliphatic acid anions in oil field waters and their contribution to the measured alkalinity

High alkalinity values found in some formation waters from Kettleman North Dome oil field are due chiefly to acetate and propionate ions, with some contribution from higher molecular weight organic acid ions. Some of these waters contain no detectable bicarbonate alkalinity. For waters such as these, high supersaturation with respect to calcite will be incorrectly indicated by thermodynamic calculations based upon carbonate concentrations inferred from traditional alkalinity measurements     

An evaluation of fluidized bed combustor ash as a source of alkalinity to treat toxic rock materials

The coal mining industry is in need of effective, locally available, low-cost ameliorants that can be used to treat the toxic materials generated by surface mining and coal cleaning plants. Ashes generated by fluidized bed combustors may locally fit these criteria. Samples of fly ash and bottom ash were acquired from facilities in West Virginia, Texas, and California and evaluated for their ability to generate alkalinity. The results show that FBC ash has the potential to produce solutions of high alkalinity depending on the CaO and CaCO₃ contents. The relative content of CaO, and to a lesser extent Ca(OH)₂, determines the rate at which alkalinity will be produced. The neutralization potential is the best parameter to evaluate the potential of an FBC ash to produce alkalinity. Because the composition of ashes from a facility vary over time and because no single parameter will accurately evaluate the rate at which alkalinity will be produced, the rate of alkaline production must be evaluated by controlled leach experiments.     

Chemical variability in the Sacramento River and in Northern San Francisco Bay

Specific conductance and concentrations of alkalinity, dissolved silica, nitrate, and ammonium were measured daily in the Sacramento River flow to northern San Francisco Bay during the rainfall seasons of 1983 and 1984 (high flow) and during late summer and early fall of 1984 (low flow). Flow and concentrations of chemical species varied in response to storm events during high flow, but flow was more variable than concentrations of chemical species. Runoff from agriculturally developed areas appeared to increase specific conductance and concentrations of alkalinity during high flow. During low flow, inputs of agricultural tailwaters caused variations in concentrations of alkalinity and dissolved silica. Dilution of municipal waste by river flow caused variability in concentrations of ammonium during both high flow and low flow. Distributions of alkalinity, dissolved silica, nitrate, and ammonium were measured in northern San Francisco Bay during late summer and fall of 1984. Changes in distributions of alkalinity in the estuary were caused by variations in alkalinity in the Sacramento River. Changes in distributions of dissolved silica, nitrate, and ammonium appeared to be primarily related to variations in supply by the river and removal by phytoplankton. Effects of removal by phytoplankton were large for ammonium and dissolved silica, but appeared relatively small for nitrate.     

Alkalinity buildup during silicate weathering under a snow cover

Results from the study of experimental plots at Hubbard Brook, New Hampshire for the years 1987, 1988, 1993, 1994, 1995, and 1996 show that the water draining from under a plot planted with pine trees exhibits its highest alkalinity during the year at about the time of spring snowmelt. This high alkalinity is believed to be due to buildup during the winter under a snow cover. The soil solutions are protected from acidic precipitation by the snow, and the natural process of the reaction of organic acids and carbonic acid with minerals and exchange complexes to form dissolved HCO₃ ^– (and organic anions) proceeds with an increase in alkalinity through the winter. When the snow melts the acidic meltwater mixes with, neutralizes and displaces the water previously occupying the soil interstices. This leads to a decided drop in alkalinity of the drainage water. The alkalinity buildup under the pine plot was found to be two to ten times greater than under a similar plot containing no higher plants. This strongly emphasizes the important role of plants, in their ability to produce organic acids and high levels of CO₂, in accelerating the weathering of silicate minerals.     

Ecological characteristics of Vrishabhavathy River in Bangalore (India)

River Vrishabhavathy, a tributary of Cauvery River was studied for 12 physico-chemical parameters at four sites over a distance of 50 km for a period of 2 years (1999–2001) at monthly intervals. Water was faintly alkaline, with pH showing negative correlation with temperature. The dissolved oxygen content increased downstream with negative correlation to biological oxygen demand (BOD), chemical oxygen demand (COD) and turbidity. Bicarbonate alkalinity was very low compared with carbonate alkalinity. Carbonate alkalinity, total hardness, total dissolved solids, total suspended solids, electrical conductivity, BOD and COD decreased downstream, with an upward trend in the middle reaches due to the introduction of raw sewage. The seasonal and yearly trends are also discussed. The river is a sewer collector undergoing self-purification.