过氧化氢存在下HCFC－22光解特性

模拟大气条件研究了ＨＣＦＣ－２２＋Ｈ２Ｏ２在有氧或无氧存在下用低压汞灯进行辐照，在２０ｍ的长光程池中用富里叶红外光仪测量其化学产物，结果表明在没有氧情况下产物为ＣＯＦ２、ＣＯ２、ＨＦ和ＨＣｌ；有氧存在时产物为ＣＯ２、Ｈ２Ｏ、ＨＦ和ＨＣｌ．从这些产物推出其可能的光解机理．     

过氧化氢存在下HCFC－22光解特性

模拟大气条件研究了ＨＣＦＣ－２２＋Ｈ２Ｏ２在有氧或无氧存在下用低压相进行辐照,在２０ｍ的长光程池中用富里叶红外光仪测量其化学产物,结果表明在没有氧情况下产物为ＣＯＦ２,ＣＯ２,ＨＦ和ＨＣｌ;有氧存在时产物为ＣＯ２,Ｈ２Ｏ,ＨＦ和ＨＣｌ。从这些产物推广其可能的光解机理。     

不同离子在CCl4引发自由基反应中的作用及其环境生物学意义

报道了一种简便的ＣＣ１４体外引发自由基反应的模型，以小鼠肝匀浆脂质过氧化产物丙二醛（ＭＤＡ）的ＯＤ５３２ｍｍ值（ＭＤＡ－ＯＤ５３２ｍｍ）作为测定自由基反应的间接指标，研究了Ｈｇ＾２＋、Ｍｎ＾２＋、Ｎｉ＾２＋、Ｃｒ＾３＋、ＳｅＯ３＾２－等离子和Ｓs２Ｏ３水溶液在ＣＣ１４引发自由基反应体系中的作用。结果表明：Ｍn＾２＋能显著抑制自由基的生成，Ｃr＾３＋有一定的抑制作用，而ＨgＴ＾２＋对自由基产生有明显促进     

OH自由基引发光氧化氟氯碳化合物的研究

研究了ＣＦＣ－１１＋Ｈ２Ｏ２，ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２，ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋Ｈ２Ｏ２＋Ｏ２４个体系的光化学反应，这些体系在低压尔照射下，Ｈ２Ｏ２产生了ＯＨ自由基，ＯＨ自由基能引发ＣＦＣ的光氧化反应，其产物在２０ｍ长的漪避用富叶红外光谱仪测量，发现在ＣＦＣ－１１＋Ｈ２Ｏ２和ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２体系中有ＣＯＦＣｌ，ＣＯ２和ＨＣｌ，而在ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋     

用电子自旋探针研究水泥固化土壤中镉离子的反应

应用电子自旋探针（Ｅｌｅｃｔｏｒｏｎ ｓｐｉｎ ｐｒｏｂｅ，简ＥＳＰ）Ｍｎ＾２＋离子的超精细结构（ｈｙｐｅｒｆｉｎｅ ｓｔｒｕｃｔｕｒｅ，简称ｈｆｓ），揭示了水泥固化土壤中Ｃｄ＾２＋离子的化学反应，研究发现：由于水泥水化产生高的ＰＨ值，Ｃｄ＾２＋离子与ＯＨ＾－离子反应生成Ｃｄ（ＯＨ）２沉‘当有ＣＯ２气体存在时，Ｃｄ＾２＋离子会与ＣＯ２和水泥水化的ＯＨ＾－离子反应生成ＣｄＣＯ３、Ｃｄ（ＯＨ）２，这些     

多级联合处理二甲基二硫醚生产废气

对二甲基二硫醚生产过程中产生的含硫有机恶臭气体采用冷冻回收、氧化吸收、吸附净化等方法进行联合处理 ,该废气处理方法建设周期短 ,投资小 ,见效快 ,具有较好的经济效益 ,两年内即可收回全部投资。实施运行后 ,大大改善了厂内及其周边大气环境。     

快速测定废水中CODcr的方法

以ＣｕＳＯ４－ＫＡｌ（ＳＯ４）２－ＮａＭｏＯ４作催化剂，在Ｈ２ＳＯ４－Ｈ３ＰＯ４体系中快速测定废水ＣＯＤｃｒ新方法，回流时间由标准法的２ｈ缩短至０．５ｈ，以ＡｇＮＯ３－ＣｒＫ（ＳＯ４）代替Ｈｇ２ＳＯ４消除ＣＩ＾－干扰，避免汞的污染。     

黄海西部大气湿沉降(降水)的pH与主要酸碱离子的关系

对黄海西部的千里岩、青岛的麦岛两个降消要样点１９９７、１９９８丙年所收集的１１３个降 Ｈ＾＋、ＮＨ４＾＋、Ｋ＾＋、Ｎａ＾＋、Ｃａ＾２＋、Ｍｇ＾２＋、Ｆ＾－、Ｃｌ＾－、ＮＯ３＾－、ＳＯ４＾２－共１０种离子成分的含量，分别用ＮＡ＾＋、Ｍｇ＾２＋、Ｃａ＾２＋＋ＮＨ４＾＋）／（ＮＯ３＋ｎｓａＳＯ４＾２－、ｃｍｓｓＳＯ４＾２－（ｎｓｓＳＯ４＾２－）的相关分析。结果表明：（１）以Ｍｇ＾２＋作为参考元素计算得到     

胶洲湾海水中二甲基硫的测定

对胶州湾海域二甲基硫进行了两年的季节监测，海水中ＤＭＳ浓度在０．０６－８．９７ｎｍｏｌ／Ｌ范围内，春季最大，而冬季最小，呈明显的季节变化，春季最大值（平均值为５．８５ｎｍｏｌ／Ｌ和６．５８ｎｍｏｌ／Ｌ）与冬季最小值（平均值为１．４０ｎｍｏｌ／Ｌ）之比约为４。胶州湾海域ＤＭＳ海气排放通量在１．７０－７．９７μｍｏｌ／（ｍ＾２·ｄ）范围内，亦呈明显的季节变化。     

前沟藻(Amphidinium hoefleri)和角刺藻(Chaetoceros gracilis)二甲基硫生产的实验研究

用实验室模拟的方法着重研究硅藻的角刺藻（Ｃｈａｅｔｏｃｅｒｏｓｇｒａｃｉｌｉｓ）和浮游甲藻的前沟藻（Ａｍｐｈｉｄｉｎｉｕｍｈｏｅｆｌｅｒｉ）生长过程中ＤＭＳ的生产及不同氮营养条件下对前沟藻ＤＭＳ生产的影响．结果表明：（１）前沟藻和角刺藻都可以生产二甲基硫（ＤＭＳ），但２者ＤＭＳ生产能力有很大差别，前沟藻ＤＭＳ平均生产率大约是角刺藻的１００倍．（２）不同生理阶段的ＤＭＳ产量不同．对数增长期的前沟藻细胞释放ＤＭＳ的能力最强，其ＤＭＳ速率是指数增长期的３倍．静止期和衰老期的前沟藻细胞ＤＭＳ的生产能力下降．（３）低氮条件对前沟藻细胞ＤＭＳ有促进作用．其中低浓度组（０．５ｍｇ／ＬＮａＮＯ３）ＤＭＳ产率是高浓度组（５０ｍｇ／Ｌ）的４倍．     

水稻土中甲硫氨酸分解释放挥发性含硫气体的影响因素

为了探讨水稻土中含硫气体产生和释放的途径 ,在室内培养条件下 ,测定了南京水稻土中含硫气体的释放 .从该淹水土壤中测出 3种含硫气体 ;羰基硫 (COS)、二甲基硫 (DMS)和少量硫化氢 (H₂S)气体 .当土壤中加入甲硫氨酸后 ,DMS气体的释放量有了明显增加 ,此外还有大量甲硫醇 (CH₃SH)和二甲基二硫 (DMDS)气体测出 .而 COS在好氧条件 (普通大气淹水 )下的释放量明显增加 ,在厌氧条件 (充氮淹水 )下的释放量变化不明显 ;只有 H₂S的释放量几乎没变 .这些结果表明 ,甲硫氨酸的分解可能是 COS、DMS、CH₃SH和 DMDS的产生源之一 ,且释放含硫气体的种类明显不同于胱氨酸和半胱氨酸 .在好氧 (普通大气 )条件下 ,DMDS和 CH₃SH的释放量低于厌氧情况 (充氮气 )下的释放量 ,DMS则高于厌氧条件下的释放量 .这表明 ,水稻土中甲硫氨酸分解产生 DMDS和 CH3SH需较强的还原条件 ,产生这 2种气体的微生物需要严格的厌氧条件 .产生 DMS的微生物则比前者需要高一些的含氧量 .土壤 pH值和含水量及光照对甲硫氨酸分解释放含硫气体均有影响 .各含硫气体在持水率 50%、普通大气、光照条件下的释放量明显高于无光照条件下的释放量 .     

The near U.V. absorption spectra of dimethyl sulfide,diethyl sulfide and dimethyl disulfide at T=300 K

Absorption cross-sections are reported for dimethyl sulfide (CH₃SCH₃), diethyl sulfide (C₂H₅SC₂H₅), and dimethyl disulfide (CH₃SSCH₃) at wavelengths greater than 200 nm, a temperature of 300 K, and a nominal spectral resolution of 0.10 nm. In general, the results are in good agreement with previous measurements of the spectra of these molecules, but are of higher precision and resolution than past measurements. New features in the spectra, including a previously unobserved vibrational progression for diethyl sulfide, are discussed. Finally, the data are used to calculate a photodissociation lifetime for dimethyl disulfide, the only one of the three molecules that absorbs light in the actinic u.v. region of the spectrum. Loss of dimethyl disulfide by photodissociation is expected to be 5 – 10 times slower than loss due to reaction of the compound with OH under atmospheric conditions.     

生物滴滤塔净化含硫混合废气

利用甲硫醚(DMS)降解菌Alcaligenes sp.SY1和丙硫醇(PT)降解菌Pseudomonas putida.S-1强化生物滴滤塔(BTF)处理DMS和PT的混合废气,研究了其挂膜启动及稳定运行阶段的降解性能,并考察了该系统同时去除H2S的能力.结果表明,BTF在DMS和PT进口浓度均为50 mg·m-3,EBRT为30 s的条件下,运行11 d即可完成挂膜启动,填料上的生物量明显增加,DMS、PT的去除率分别可达到90%和100%.系统稳定运行时,DMS和PT的最大去除负荷分别为8.7 g·(m~3·h)~(-1)和12.4 g·(m~3·h)~(-1),PT的去除效果更佳.DMS和PT混合废气在降解过程中,PT对DMS的降解有较明显的抑制作用,当PT进气浓度大于51 mg·m-3时,DMS的去除效率下降.BTF还能同时有效去除H2S,当混合废气中H2S浓度达到230 mg·m-3时,H2S去除率仍能高达98%,但是115 mg·m-3以上的H2S会对DMS的降解产生不利影响.     

Effect of liming on sulfate transformation and sulfur gas emissions in degraded vegetable soil treated by reductive soil disinfestation

Reductive soil disinfestation (RSD), namely amending organic materials and mulching or flooding to create strong reductive status, has been widely applied to improve degraded soils. However, there is little information available about sulfate (SO₄^2 −) transformation and sulfur (S) gas emissions during RSD treatment to degraded vegetable soils, in which S is generally accumulated. To investigate the effects of liming on SO₄^2 − transformation and S gas emissions, two SO₄^2 −-accumulated vegetable soils (denoted as S1 and S2) were treated by RSD, and RSD plus lime, denoted as RSD₀ and RSD₁, respectively. The results showed that RSD₀ treatment reduced soil SO₄^2 − by 51% and 61% in S1 and S2, respectively. The disappeared SO₄^2 − was mainly transformed into the undissolved form. During RSD treatment, hydrogen sulfide (H₂S), carbonyl sulfide (COS), and dimethyl sulfide (DMS) were detected, but the total S gas emission accounted for < 0.006% of total S in both soils. Compared to RSD₀, lime addition stimulated the conversion of SO₄^2 − into undissolved form, reduced soil SO₄^2 − by 81% in S1 and 84% in S2 and reduced total S gas emissions by 32% in S1 and 57% in S2, respectively. In addition to H₂S, COS and DMS, the emissions of carbon disulfide, methyl mercaptan, and dimethyl disulfide were also detected in RSD₁ treatment. The results indicated that RSD was an effective method to remove SO₄^2 −, liming stimulates the conversion of dissolved SO₄^2 − into undissolved form, probably due to the precipitation with calcium.     

介质阻挡放电降解流动态二甲基二硫废气

采用介质阻挡放电等离子体技术(Dielectric Barrier Discharge,DBD)处理常压下流动态气体中的有机硫恶臭气体二甲基二硫(Dimethyl Disulfide,DMDS).研究了不同停留时间、进气浓度及外施电压条件下DMDS的转化,推导了DBD处理DMDS的动力学模型,并根据傅立叶红外(FT-IR)产物分析探讨了反应机理.研究结果表明,DMDS降解产物主要为CO2、SO2和H2O.在停留时间0.067 s、外施电压7500 V、进气量8.4m3·h-1的条件下,进气浓度为80 mg·m-3 DMDS的降解率达到64.3%,体积降解比量为2.26×10-2L·s-1·W-1,绝对处理量达到430 mg·h-1.     

小麦田中有机硫气体的释放

采用密闭箱法对不同施肥条件下小麦田中羰基硫(COS)、二硫化碳(CS₂)和二甲基硫(DMS)的释放情况进行了监测.结果表明,小麦生长过程对COS、CS₂和DMS释放影响显著,小麦对COS有明显吸收作用,DMS和CS₂是麦田中释放的主要含硫气体.COS和CS₂释放速率昼夜变化明显.仅施用有机肥的麦田,硫释放总量高于其它田块.不同施肥条件的田块,硫释放总量范围在-1.40～0.79mg·ml^-2之间.     

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin(2,3,7,8-TCDD) is an efcient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2 O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus(RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 × 10 20cm3/(mole·sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.     

Perturbations to tropospheric oxidants, 1985–2035: 2. Calculations of hydrogen peroxide in chemically coherent regions

Increasing global emissions of trace gases NO, CH₄, and CO, along with perturbations initiated by changes in stratospheric O₃ and H₂O, may cause tropospheric hydrogen peroxide (H₂O₂) levels to change. Specific scenarios of CH₄CONO emissions and global climate changes are used to predict HO₂ and H₂O₂ changes from 1985 to 2035 in a one-dimensional model that simulates different chemically coherent regions (e.g. urban, non-urban continental and marine mid-latitudes; marine and continental low latitudes).If CH₄ and CO emissions continue to increase throughout the troposphere at current rates (1% yr⁻), there will be large increases in H₂O₂, for example, more than 100% in the urban boundary layer from 1985 to 2035. Globally, H₂O₂ will increase 22% with HO₂ increasing 8% and O₃ increasing 13%. When CH₄, CO and NO emissions are specified on a regionally varying basis and are parameterized for high and low potential growth rates, globally averaged increases in surface concentrations are 12% for H₂O₂ and 18% for O₃. A global warming (with increased H₂O vapor) or stratospheric O₃ depletion superimposed on CH₄, CO and NO emissions changes will cut O₃ increases but add to peroxide, increasing levels as much as 150% above present day in some regions.Both globally uniform and region-specific scenarios predict a 10–15% loss in global OH from 1985 to 2035. Thus, conversion of OH to HO₂ and H₂O₂ in the atmosphere may signify a loss of gaseous oxidizing capacity in the atmosphere and an increase in aqueous-phase oxidizing capacity.     

光助-二茂铁/H2O2非均相体系降解磺胺二甲基嘧啶

抗生素在废水和地表水中经常检出,因其可诱导细菌菌群的抗药性而备受关注,因而亟需发展新型高效的抗生素去除技术.本研究构建了基于二茂铁(Fc)的光助非均相氧化体系,并选取水体中广泛检出的磺胺二甲基嘧啶(SMZ)为模型化合物,研究了SMZ在该体系中的降解动力学、转化途径和产物.结果表明,相对于Fc、Fc+UV、H_2O_2、H_2O_2+UV、Fc+H_2O_2体系,SMZ在Fc+H_2O_2+UV体系中呈现更好的降解效率.自由基淬灭实验证实·OH是Fc+H_2O_2+UV体系中决定SMZ降解的最主要活性物种.电子自旋共振实验发现Fc+H_2O_2+UV体系中产生了超氧自由基阴离子,说明Fc在光照条件下可产生电子. H_2O_2接受电子后歧化产生·OH进而促进SMZ降解.采用轨道离子阱高分辨质谱对SMZ在Fc+H_2O_2+UV体系中的降解产物进行了鉴定,发现有SMZ的羟基化、脱SO_2和C—S、S—N及N—C键断裂的产物形成.水中常见溶解性组分,如DOM、Cl~-及Br~-,可淬灭·OH而抑制SMZ降解,但离子强度对SMZ在Fc+H_2O_2+UV体系中的降解无显著影响,说明该技术对于含有高盐度抗生素废水的处理仍具有较好的效果.     

外源含硫化合物对土壤挥发性有机硫化合物交换通量的影响

通过静态箱采样和Entech7100预浓缩仪-GC-MS分析了半胱氨酸、硫化钠和硫酸钠对土壤吸收或释放羰基硫（COS）、二甲基硫醚（DMS）、二硫化碳（CS2）和二甲二硫醚（DMDS）等4种挥发性有机硫化合物（VOSCs）的影响.结果表明,添加半胱氨酸后,土壤由COS和CS2汇转变为源,DMS和DMDS通量显著增加,且...