汉江上游金水河流域河水的化学特征

本文以汉江上游金水河流域为研究区域,通过对大气降水、河水的水化学及氢氧稳定同位素分析,揭示河水水化学特征及其补给来源.结果表明,(1)流域内大气降水和河水的水化学类型为Ca2+-HCO3-型,主要占优势的阴阳离子分别为HCO3-和Ca2+;(2)河水水质总体表征良好,其离子、金属及微量元素和营养盐的含量较低;(3)河水的δD和δ18O关系表明,河流的主要补给来源为大气降水.     

黄河下游地区河水主要离子和锶同位素的地球化学特征

对黄河下游地区河水主要阴阳离子、锶元素及其同位素组成进行了分析.结果发现其水化学组成主要以Ca~(2+),Na~+,HCO_3~-和SO_4~(2-)离子为主,分别占阴阳离子组成的75%以上.干流与支流间在化学组成上存在显著差异,黄河干流的SO_4~(2-),NO_3~-和Cl~-具有共同的来源,而支流河水中的SO_4~(2-),NO_3~-和Cl~-来源不同.黄河下游具有较高的锶含量及较低的锶同位素组成,锶含量变化范围在0.0429 mg·l~(-1)-0.936mg·l~(-1)之间,平均含量为0.394 mg·l~(-1),锶同位素组成变化范围在0.70986-0.71139之间,平均值为0.71118,其中黄河人海口的锶同位素组成(~(87)Sr/~(86)Sr=0.70986)与现代海水锶同位素比值(0.70916)相近,表明其锶同位素组成受海水作用影响较大.对主要元素、微量元素锶及其同位素组成分析研究发现,黄河下游地区河水锶同位素组成主要源于蒸发盐岩和碳酸盐岩的风化溶解作用,而人类活动的影响相对较小.由锶同位素平衡方程计算得出,黄河下游地区河水锶同位素组成由大气降水和岩石风化作用混合而成,其中大气降水对黄河下游地区~(87)Sr/~(86)Sr的贡献率约为30%,而岩石风化对其贡献率约为70%.     

北京市大气OH自由基测量结果及其特征

利用2种基于高效液相色谱技术的大气OH测量方法测定了北京城市大气中OH自由基,得到了其浓度水平和日变化情况.测得夏季日间最大OH浓度为～8×10⁷ cm^-3,秋季日间最大浓度为2×10⁷～4×10⁷cm^-3,并根据同步测量光强和其它污染物的浓度,分析了OH浓度与这些条件的相关性.结果表明,OH浓度与UV-B相对强度、O₃和HNO₂的浓度具有一定的正相关性     

成都市地表水天然水化学变化特征及影响因素

为揭示大型城市对地表水天然水化学的影响,于2019年春开始对长江上游岷、沱江流域成都段河流进行了每月采样监测,同时采集成都市57个污水处理厂进出口水样,测试所有样品的主要离子等水化学参数,并与搜集的历史岷、沱江数据对比.结果表明,成都地表水天然水化学目前仍是中-低矿化度水,水化学类型为重碳酸盐钙组水,是流域碳酸盐岩风化作用决定的天然水化学特征,同时受硅酸盐和蒸发岩风化的影响.成都地表水天然水化学表现出明显的月变化特征,即枯水期主要离子和矿化度质量浓度高而丰水期质量浓度低,反映出点源影响特征;空间上城市下游主要离子和矿化度高于城市上游,而且支流流域高于干流流域,反映出明显的城市影响.模拟计算等进一步分析显示,城市活动是成都地表水天然水化学变化的主要驱动因素,表现在污水排放对水体Cl^-和Na⁺升高的显著贡献,和人为酸性气体排放导致的水体总硬度/碱度>1.对比岷、沱江20世纪60年代天然水化学数据说明,目前水体Cl^-/Na⁺比已显著升高,尽管水体尚未出现天然水化学性质的根本变化,但已表现出一定的盐渍化趋势.作为距长江源头最近的特大型城市,成都市对长江水系天然水化学的影响及其环境效应值得进一步关注.     

升金湖河湖交汇区地表-地下水水化学特征及成因分析

以升金湖河湖交汇区为研究区,测试不同类型水体水化学组成和氢氧同位素值,分析其季节变化特征,探究地表-地下水中化学离子来源,最后估算混合水源对地下水中化学离子的贡献量.结果表明：①研究区地表-地下水主要离子浓度均高于大气降水,理化参数呈现季节变化特征;②地表水以Ca-HCO₃类型水为主,且在夏季占比明显高于其他季节,而地下水以Ca-HCO₃和Ca-SO₄类型水为主,占比分别为46%和27%,且季节差别不显著;③地表-地下水中Ca²⁺和Mg²⁺主要来自于碳酸盐岩的溶解,且有碳酸和硫酸参与了碳酸盐矿物溶解的过程,Na⁺和Cl^-除来源于大气降水外,还来源于当地农业施肥和粪便污水;④水源混合也是地下水化学离子的一个重要来源,其对Cl^-的贡献率平均达到28%,且呈现季节变化趋势.     

A Comparison of Loch Chemistry from 1955 and 1999 in the Cairngorms,N.E. Scotland

The Cairngorms in north-east Scotland is remote from pollutant sources although it currently receives ca. 10 kg ha¹ yr¹ S and ca. 11 kg ha¹ yr¹ N deposition from the atmosphere.In 1955, 15 lochs (lakes) at a range of altitudes were sampled and analysed for major ion concentrations. A new survey of these and an additional 23 lochs and their catchment soils was conducted in 1999 to determine the impact of acid deposition, and the changes in loch chemistry since the 1955 survey. The bedrock geology of this region has a strong influence on the loch chemistry. Surface waters were generally more acidic in high altitude areas due to predominantly poorly buffered, thin alpine soils developed on granitic parent material (mean acid neutralising capacity (ANC) for 23 lochs = 30 eq L¹). At lower altitudes where the geology is dominated by Dalradian metamorphic rocks surface waters are comparatively base rich and have higher ANC (mean ANC for 15 lochs = 157 eq L¹). Surface water nitrate concentrations show a negative relationship with soil C:N status, in that higher nitrate only occurs at low soil C:N ratios. A comparison of data for 1955 and 1999 shows that sulphate concentrations are significantly lower (67.8 and 47.5 eq L¹, respectively), and pH has improved (pH 5.6 and 5.9) in response to decreased S deposition since the mid 1970s. However, mean nitrate concentrations were found to increase from 2.48 >eq L¹ in 1955 to 5.65 eq L¹ in 1999. Differences in the sampling and laboratory methods from 1955 and 1999 are acknowledged in the interpretation of data.     

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.