A kinetic study of phenol nitration and nitrosation with nitrous acid in the dark

We studied the transformation of phenol in the presence of nitrous acid in the dark. The main detected intermediates were 2-nitrophenol, 4-nitrophenol and 4-nitrosophenol. For the first time a kinetic analysis of the reaction in a pH interval relevant to environmental chemistry has been carried out. The kinetic data are consistent with phenol transformation being initiated by HNO₂. The results are relevant to the chemistry of the atmosphere, where HNO₂ forms upon heterogeneous conversion of ^·NO₂, and to water treatment techniques.     

The U.S. Experience in Promoting Sustainable Chemistry (9 pp)

- Sustainable chemistry - Section editors: Klaus Günter Steinhäuser, Steffi Richter, Petra Greiner, Jutta Penning, Michael AngrickBackground, Aim and Scope Recent developments in European chemicals policy, including the Registration, Evaluation and Authorization of Chemicals (REACH) proposal, provide a unique opportunity to examine the U.S. experience in promoting sustainable chemistry as well as the strengths and weaknesses of existing policies. Indeed, the problems of industrial chemicals and limitations in current regulatory approaches to address chemical risks are strikingly similar on both sides of the Atlantic. We provide an overview of the U.S. regulatory system for chemicals management and its relationship to efforts promoting sustainable chemistry. We examine federal and state and examine lessons learned from this system that can be applied to developing more integrated, sustainable approaches to chemicals management.Main Features There is truly no one U.S. chemicals policy, but rather a series of different un-integrated policies at the federal, regional, state and local levels. While centerpiece U.S. Chemicals Policy, the Toxic Substances Control Act of 1976, has resulted in the development of a comprehensive, efficient rapid screening process for new chemicals, agency action to manage existing chemicals has been very limited. The agency, however, has engaged in a number of successful, though highly underfunded, voluntary data collection, pollution prevention, and sustainable design programs that have been important motivators for sustainable chemistry. Policy innovation in the establishment of numerous state level initiatives on persistent and bioaccumulative toxics, chemical restrictions and toxics use reduction have resulted in pressure on the federal government to augment its efforts.Results and Conclusions It is clear that data collection on chemical risks and phase-outs of the most egregious chemicals alone will not achieve the goals of sustainable chemistry. These alone will also not internalize the cultural and institutional changes needed to ensure that design and implementation of safer chemicals, processes, and products are the focus of the future. Thus, a more holistic approach of ‘carrots and sticks’ – that involves not just chemical producers but those who use and purchase chemicals is necessary. Some important lessons of the US experience in chemicals management include: (1) the need for good information on chemicals flows, toxic risks, and safer substances.; (2) the need for comprehensive planning processes for chemical substitution and reduction to avoid risk trade-offs and ensure product quality; (3) the need for technical and research support to firms for innovation in safer chemistry; and (4) the need for rapid screening processes and tools for comparison of alternative chemicals, materials, and products.     

ESTIMATED BACKGROUND CONCENTRATIONS OF SULFATE IN DILUTE LAKES1

ABSTRACT: Lake water sulfate values were examined for two areas in western Norway and the western United States presently receiving low levels of sulfate in atmospheric deposition. Data from these areas were used to estimate background concentrations of sulfate in lakes found in areas currently receiving acidic deposition. The two areas contain dilute lakes with concentrations of sea-salt corrected Ca+ Mg less than 50 μeq/l or conductivity < 10μS cm^-1and receive precipitation with volume-weighted mean pH > 4.8. Based on observations from these areas, we conclude that background sulfate concentrations were probably no more than 10 to 15 μeq L^-1for areas of Norway and the U.S. containing lakes with low concentrations of base cations. For southern Norway and the northeastern U.S., present lakewater sulfate concentrations represent an increase of 7 to 10 fold above these estimated background values.     

Carbonyl products of the gas-phase reaction of ozone with 1-alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas-phase reaction of ozone with the 1-alkenes (RCH = CH 2) 3-methyl-l-butene (R = i-propyl), 4-methyl-l-pentene (R = i-butyl), 3-methyl-l-pentene (R= s-butyl), 3,3-dimethyl-l-butene (R = t-butyl) and styrene (R = C₆H₅) at ambient T and p = 1 atm of air. Sufficient cyclohexane was added to scavenge OH in order to minimize reactions of OH with the alkenes and with their carbonyl products. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃ + RCH = CH₂ → α(HCHO + RCHOO) + (1 - α) (H₂COO + RCHO), where formaldehyde and RCHO are the primary carbonyls and H₂COO and RCHOO are the biradicals. Measured sums of the primary carbonyl formation yields were 1.006 ± 0.053 (1 S.D.) for formaldehyde + methylpropanal from3-methyl-l-butene(α = 0.494 ± 0.049), 1.025 ± 0.017 for formaldehyde + 2-methylbutanal from 3-methyl-l-pentene (α = 0.384 ± 0.013),1.147 ± 0.050 for formaldehyde + 3-methylbutanal from 4-methyl-l-pentene (α = 0.384 ± 0.020), 0.986 ± 0.014 for formaldehyde + 2,2-dimethylpropanal from 3,3-dimethyl-l-butene (α = 0.320 ± 0.012) and 0.980 ± 0.086 for formaldehyde + benzaldehyde from styrene (α = 0.347 ± 0.059). Carbonyls other than the primary carbonyls were identified; formation pathways are proposed that involve subsequent reactions of the monosubstituted biradicals RCHOO. Similarities and differences between branched-chain 1-alkenes and n-alkyl-substituted 1-alkenes are discussed.     

多核聚合形态Al30混凝控制水中腐殖酸与残留铝的研究

制备了优势形态为Al30的聚合铝PAC-Al30,与优势形态为Al13的常用聚合铝PAC-Al13及AlCl3作对比实验,考察了不同铝系混凝剂强化混凝控制水中腐殖酸(Humic Acid,HA)和残留铝的差异.结果表明,PAC-Al30具有足够的稳定性,与PAC-Al13和AlCl3相比,PAC-Al30可以更好地控制出水腐殖酸和残留铝浓度,且以碱化度B为2.4的PAC-Al30效果最好.PAC-Al30和PAC-Al13比AlCl3有更宽的有效投量范围,可以提高实际应用中的稳定性.Ca2 和高岭土的存在均有利于PAC-Al30混凝去除HA.低温对PAC-Al30混凝去除HA有不利影响.研究表明,Al30是一种可用于控制水中腐殖酸和残留铝的新型混凝/絮凝活性成分.     

Impacts of Rotational Grazing and Riparian Buffers on Physicochemical and Biological Characteristicsof Southeastern Minnesota, USA, Streams

We assessed the relationship between riparian management and stream quality along five southeastern Minnesota streams in 1995 and 1996. Specifically, we examined the effect of rotationally and continuously grazed pastures and different types of riparian buffer strips on water chemistry, physical habitat, benthic macroinvertebrates, and fish as indicators of stream quality. We collected data at 17 sites under different combinations of grazing and riparian management, using a longitudinal design on three streams and a paired watershed design on two others. Continuous and rotational grazing were compared along one longitudinal study stream and at the paired watershed. Riparian buffer management, fenced trees (wood buffer), fenced grass, and unfenced rotationally grazed areas were the focus along the two remaining longitudinal streams. Principal components analysis (PCA) of water chemistry, physical habitat, and biotic data indicated a local management effect. The ordinations separated continuous grazing from sites with rotational grazing and sites with wood buffers from those with grass buffers or rotationally grazed areas. Fecal coliform and turbidity were consistently higher at continuously grazed than rotationally grazed sites. Percent fines in the streambed were significantly higher at sites with wood buffers than grass and rotationally grazed areas, and canopy cover was similar at sites with wood and grass buffers. Benthic macroinvertebrate metrics were significant but were not consistent across grazing and riparian buffer management types. Fish density and abundance were related to riparian buffer type, rather than grazing practices. Our study has potentially important implications for stream restoration programs in the midwestern United States. Our comparisons suggest further consideration and study of a combination of grass and wood riparian buffer strips as midwestern stream management options, rather than universally installing wood buffers in every instance. RID=" ID=" The Unit is jointly sponsored by the US Geological Survey, Biological Resources Division; the Minnesota Department of Natural Resources; the University of Minnesota; and the Wildlife Management Institute.     

A CHLORIDE BUDGET FOR THE MISSISSIPPI RIVER,HEADWATERS TO MOUTH1

ABSTRACT Mass budgets for chloride were estimated from 1975-1978 for the Mississippi River from headwaters to near the mouth to determine the magnitudes of natural and anthropogenic sources. Annual chloride input from precipitation ranged from about 200 kg mi^-2yr^-1 at Royalton, Minnesota, to about 350 kg mi^-2yr^-1 at Vicksburg, Mississippi. Mass export ranged from about 900 kg mi^-2yr^-1 at Royalton to about 8000 kg mi^-2yr^-1 at Vicksburg. As much as 80 percent of the residual, the difference between input and export, probably is contributed by anthropogenic sources. In particular, semi-logarithmic scatterplots of monthly total discharge against chloride concentration show that, during early spring, chloride elevations in the Mississippi River and Ohio River are elevated, possibly because of flushing of road salt and leaching of chloride from the accumulated snowpack.     

A method for double-sided friction stir spot welding

A rotating anvil similar to a pinless friction stir welding (FSW) tool can be applied to friction stir spot welding (FSSW) of thin metal plates. FSSW is a solid-state joining process that is currently being used by automotive manufacturers as an alternative to rivets and traditional resistance spot welding. The principal detractor of this process is the keyhole left by pin extraction, which can be detrimental to the weld strength. A pinless tool can be used to eliminate the keyhole. However, this approach is limited to joining thin sheet (≤1 mm). Using a rotating anvil with the FSSW process permits the joining of thicker cross sections, improves the mechanical strength of the spot weld and reduces the reaction forces on the spot welding frame. A numerical model of the process, tensile shear tests and macrosection analysis are used to evaluate the spot welds.Macrosection and numerical analysis reveals that the material flow between the pinless tool and rotating anvil is complex and unique to this process. It has been found that the use of a rotating anvil for FSSW is a viable means to create quality spot welds in thicker weldments.     

某化工企业内操职业心理现状分析与改进

通过对某化工企业室内操作人员(以下简称内操)职业心理现状进行的调查分析,追踪内操职业心理成因并提出建议与指导,通过一系列措施的制定和落实,改进管理,改善内操心境,引导内操健康生活、快乐工作。     

区域水化学条件对淮南采煤沉陷区水域沉积物磷吸附特征的影响研究

在淮南潘谢采煤沉陷区水域的潘集(PJ)、顾桥(GQ)、谢桥(XQ)各选一研究站点,研究区域水化学条件下溶液离子组分对表层沉积物磷(P)吸附特征的影响.等温吸附实验分别在纯水、NaCl、CaCl2、NaHCO3和NaHCO3+CaCl2共5组环境溶液中进行,其中前4组设置为探讨各组分对P吸附的单独作用,最后1组代表各组分的综合作用.结果表明,环境溶液设置对P的吸附特征有重要影响,Ca2+能显著增强沉积物对P的吸附潜能,而弱碱性环境(NaHCO3组)则不利于沉积物对P的吸附,实际水化学条件下的作用则表现为二者的综合,但Ca2+增强作用要显著大于碳酸盐弱碱性缓冲体系的弱化作用.3个站点沉积物P的零吸附平衡浓度(EPC0)的均值分别为0.059、0.032和0.040 mg·L-1,总体上有向水体释磷的趋势,PJ站点释放潜能要高于GQ和XQ站点,与研究水域营养水平密切相关.由于特殊的沉积环境,研究水域P释放潜能比富营养化程度较高的湖泊要弱,接近于营养水平较低的水体.