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  新《生活饮用水卫生标准》GB5749- 项目解读 一氯苯
 
1 概述

1.1物理化学性质
 
   熔点:-45.6℃,沸点:132.O℃,密度:1.1058g/L(20℃),水中溶解度:500mg/L(20℃),蒸汽压:1.18kPa(20℃),辛醇水分配系数对数值:2.84。一氯苯的味和嗅阈值为50,10—20μg/L,嗅阈值也有40-120及100μ/L的报道。
 
1.2主要用途
    一氯苯主要作为溶剂用于杀虫剂配方,或用作去油污剂,也用作合成其他卤代物的中间体。
 
1.3环境归宿
    当一氯苯释放到水中或大地时.主要由于挥发于大气中,会导致其浓度降低。在水中会发生生物降解,其进程在淡水中比在入海河口水和海水中快速。如降解微生物经过驯化,其降解速度会更快。一氯苯有时也可吸附在有机沉淀物上。在砂质土和含水层中,一氯苯是较为流动的,它会缓慢地降解进入这些土壤中;因此它会渗入地下水中。辛醇水分配系数表明少量一氯苯会存在于水生物中.有时可能不存在。
 
2 分析方法

    一氯苯的标准分析法是用己烷萃取,再用带电子捕获检测器的汽液色谱法检测。此方法应用于自来水和河水的最低检测浓度约O.1μg/L。
    方法依据:EPA502.2,524.2及卫生部《生活饮用水卫生规范》55一氯苯气相色谱法。
 
3环境水平和人体摄入水平
    一氯苯在废水、地表水、地下水和饮用水中有检测出。在一些加拿大水源中,平均浓度低于1μg/L;最大值5μg/L。由于一氯苯的易挥发性和广泛用作溶剂,使之大量释放到空气中。但是,在大气中的浓度通常很低.常低于4.6μg/m3。尽管氯苯在食用淡水乏海水生物里含量不高,但它仍可被发现。人奶对婴儿可能是一种氯苯暴露来源。在美国曾有一项研究,在8份人奶样品中,5份检测含有氯苯。尽管一氯苯在空气中的含量处于低水平,但呼吸仍是接触一氯苯的主要途径。
 
4 实验动物及人体动力学特征和代谢

    一氯苯易于通过口服和呼吸途径被吸收.并大部分积聚在脂肪组织中。哺乳类动物的一氯苯主要代谢产物是p-氯苯酚硫醚胺酸、4-氯邻苯二酚、p-氯苯酚。人类主要的代谢产物是4氯邻苯二酚。一氯苯排泄的主要途径是尿液。少量一氯苯通过粪便排泄或保留在体内。
 
5 动物实验
    急性暴露 通过对实验动物进行口服和吸人一氯苯.表明一氯苯的急性毒性较低。
    急性接触试验的主要受害的靶器官是肝脏和肾脏。
    短期暴露 小鼠13周的短期接触.影响主要作用于肝脏、肾脏和造血系统。125mg/kg体重确认为这项研究的NOAEL值。而LOAEL则是250mg/kg体重,此剂量会引起脾脏重量的轻微减轻,和胸腺、脾脏和骨髓淋巴缺损:长期暴露 大鼠、小鼠两年的研究里.低剂量未观察到一氯苯的毒性。但可确认B6c3F1雄小鼠的NOAEL是60mg/kg体重.B6C3F1雌小鼠和Fischer344雌、雄大鼠的NOAEL值是120mg/kg体重。
    生殖毒性、胚胎毒性、致畸性 让Fischer344大鼠和新西兰白兔在器官发育期每天吸入6小时的一氯苯.其浓度分别为0.75、210、590ppm(O.345、966、2714mg/m3),并没有引起对Fischer344大鼠的胚胎毒性和致畸性,但母鼠吸人浓度2714mg/m3会导致母体毒性.胎兔内脏的畸变发病率较低,而且其畸变与剂量无关。
    致突变性和相应终点 无论大鼠或仓鼠肝S9酶的活化作用是否存在,一氯苯对鼠伤寒沙门氏菌TA98、TAl00、TAl535或TAl537都没有致突变性。用含一氯苯的玉米油对5只一组的小鼠进行腹膜内注射(直到70%的LD50),会导致微核多色红细胞形成与剂量相关的增长。这种影响被认为是由于一氯苯的诱裂性造成的。
    致癌性 在两年的研究里.对两性相同数量50只为一组的Fischer344大鼠和50只为一组的B6c3F1小鼠进行103周每周j天灌饲含有一氯苯的玉米油。60或120mg/kg体重的剂量可引起雄性Fischer344大鼠肝成瘤结节发生率的轻微上升(120mg/kg体重的剂量有统计学意义)。未见雄性和雌性Fischer344大鼠的肝细胞癌发生率上升。也未见雌性Fischer344大鼠或雄性和雌性B6C3F1小鼠的肿瘤发生率上升。无迹象表明一氯苯对大鼠和小鼠有致癌性。

6对人体的影响
    一氯苯对人体是有毒的;中毒或职业性接触会引起中枢神经系统紊乱。两年长期的职业性接触一氯苯会导致头痛、头昏眼花和失眠。
 
7 国内外水质标准中一氯苯的限值
    世界各地饮用水水质标准中一氯苯的限值(μg/L)
来 源
卫生部生活饮用水卫生规范2001
世界卫生组织饮用水水质准则1996
欧盟饮用水-水质指令98/83/EC
美国现行饮用水
加拿大饮用水质标准1996
澳大利亚饮用水水质准则
日本生活饮用水水质标准2004
限值
30
300
/
健康值100
最大值100
80
300
300

8 限值
    尽管剂量的增加对雄性大鼠出现肝结节有微弱的剂量关系,但这个重要的证据表明一氯苯没有遗传毒性;因此适用TDI法确定限值。
    两年大鼠和小鼠的研究.确定了60m/kg体重是致肿瘤的NOAEL值。采用5OO个不确定因子(其中10。为种间和种内变异,5为致癌性的有限证据)每周给药5d,计算出TDI值为85.7μg/kg体重,TDI值的10%分给饮用水,得出限值为300μg/L。但是这个值远远超过一氯苯在水中的味闽值和嗅阈值下限10μg/L。

 
Synonyms Chlorobenzene
Benzene, chloro-
Benzene chloride
Monochlorobenzene
Analytical Methods EPA Method 502.2 EPA Method 503.1 EPA Method 524.1 EPA Method 524.2 EPA Method 601 EPA Method 602 EPA Method 624 EPA Method 8010B EPA Method 8020A EPA Method 8021A EPA Method 8240B EPA Method 8260A
Molecular Formula C6H5Cl
Use
Solvent for paints sometimes used in dry-cleaning chem int for phenol, o- & p-chloronitrobenzene, ddt, & aniline used in mfr of insecticides & as int in mfr of dyestuffs solvent carrier for methylene diisocyanate
 Used as a fiber swelling agent and dye carrier in textile processing, a tar and grease remover in cleaning and degreasing operations, a solvent in surface coating and surface coating removers. Used as a solvent in the manufacture of adhesives, paints, polishes, waxes, diisocyanates, pharmaceuticals, and natural rubber.
Consumption Patterns 32% FOR O- AND P-CHLORONITROBENZENES; 27% FOR PHENOL; 5% FOR DDT; 36% FOR MISC APPLICATIONS INCLUDING SYNTHESIS OF ANILINE AND USE AS A SOLVENT (1972) Solvent (pesticide formulation, TDI processing, degreasing agent), 42%; Nitrochlorobenzenes, 32%; Diphenyl oxide and phenylphenols, 15%; Miscellaneous, 11% (1985) CHEMICAL PROFILE: Monochlorobenzene. Nitrochlorobenzenes, 40%; solvent (for pesticide formulations, TDI processing and degreasing), 27%; diphenyl oxide and phenylphenols, 20%; polysulfone polymers, 5%; miscellaneous, 8%. CHEMICAL PROFILE: Monochlorobenzene. Demand: 1986: 222 million lb; 1987: 220 million lb; 1991 projected/: 195 million lb.
Apparent Color COLORLESS LIQUID
Odor FAINT, NOT UNPLEASANT ODOR ; ALMOND-LIKE ODOR ; Mild amine odor ; Mild aromatic
Boiling Point 132 DEG C
Melting Point -45.6 DEG C
Molecular Weight 112.56
Density 1.1058 @ 20 DEG C/4 DEG C
Odor Threshold Concentration Odor recognition in air: 2.10x10-1 ppm. Odor Low, 0.98 mg/cu m; Odor High, 280.0 mg/cu m
Sensitivity Data If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin. Irritation of the eyes and nose.
Environmental Impact Chlorobenzene will enter the atmosphere from fugitive emissions connected with its use as a solvent in pesticide formulations and as an industrial solvent. Once released it will decrease in concentration due to dilution and photooxidation. Releases into water and onto land will decrease in concentration due to vaporization into the atmosphere and slow biodegradation in the soil or water. Chlorobenzene would be expected to percolate into the ground water if soil is sandy and poor in organic matter. Little bioconcentration is expected into fish and food products. Primary human exposure is from ambient air, especially near point sources.
Environmental Fate TERRESTRIAL FATE: Since chlorobenzene is fairly volatile, much of it will be lost to the atmosphere . It is relatively mobile in sandy soil and aquifer material and biodegrades very slowly or not at all in these soils(2-5). Therefore, it can be expected to leach into the groundwater. It has a moderate adsorption onto organic soil and if retained long enough it will biodegrade and even mineralize in soil(6). Degradation will generally be slow, but fairly rapid mineralization (20%/week) has been reported in one study(7). Acclimation of soil microorganisms is an important factor(8). AQUATIC FATE: The primary loss will be due to evaporation. The rate of evaporation will depend on the wind speed and water movement. The half-life for evaporation is approximately 4.5 hours with moderate wind speed . Biodegradation will occur during the warmer seasons and will proceed more rapidly in fresh water than in estuarine and marine systems(2,3). The rate will also depend on the acclimation of microbial communities to chlorobenzene or related chemicals. One reported half-life for an estuarine river with near natural conditions (22 deg C) is 75 days . A moderate amount of adsorption will occur onto organic sediments . ATMOSPHERIC FATE: Reaction with hydroxyl radicals is the dominant removal mechanism with an estimated half-life of 9 days with the formation of chlorophenols . Reaction in polluted air with nitric oxide is somewhat faster and produces chloronitrobenzene and chloronitrophenols . Photolysis would proceed at a much slower rate, with monochlorobiphenyl being produced .
Drinking Water Impact DRINKING WATER: 1975 USEPA National Organics Reconnaissance Survey (NORS) finished drinking water samples: Miami, FL - 1 ug/L; Seattle, WA - not detected (detection limit not reported); Cincinnati, OH - 0.1 ug/L; Ottumwa, IA - not detected; and Philadelphia, PA - <0.1 ug/L . Finished water in 9 of 10 supplies surveyed by the USEPA contained chlorobenzene with 5.6 and 4.7 ppb in Terrebonne Parish, LA and New York City, respectively(7). Chlorobenzene may be formed during chlorination(7). GROUNDWATER: As of June 30, 1984 - Wisconsin, 1174 community wells, 0% pos; 617 private wells, 0% pos, detection limit 1.0-5.0 ug/L . During 1981-1982, 945 wells scattered throughout the USA, 0.1% pos., concn detected 2.7 ug/L, detection limit 0.5 ug/L(8). 14 ppt (Zurich, 1973) under densely populated, partly industrial area . SURFACE WATER: Ohio River Basin (large survey, 1980-1981) detected in 9.6% of samples, but only 0.01% were >1 ppb. Maximum concentration was >10 ppb . In 14 Industrial River Basins (1975-76), only 5% of samples in the range 1-4 ppb . SEAWATER: Not detected in Raritan Bay (Lower Hudson)(6). Monochlorobenzenes were detected in groundwater in Miami, FL at a concn of 1.0 mg/l. Monochlorobenzenes were detected in raw water contaminated with municipal waste in Philadelphia, PA at concn of 0.1 mg/l. Monochlorobenzenes were detected in raw water contaminated with industrial discharge in Cincinnati, OH and Lawrence, MA at concn of 0.1-0.5 mg/l and 0.12 mg/l, respectively. EFFL: Monochlorobenzenes were detected in industrial discharge in Lawsons Fork Creek, SC at a concn of 8.0-17.0 mg/l. Monochlorobenzenes were detected in the municipal water in Coosa River, GA at a concn of 27.0 mg/l. The concentrations of volatile organic chemicals in the air of three wastewater treatment plants, were compared on the basis of samplings carried out with charcoal tubes during a period of 7 consecutive days. Combustible organic vapor content was determined with an organic vapor analyzer provided with a flame ionization detector. The highest organic vapor concentrations (300 ppm) in the air were recorded at the plant that was processing the highest proportion of industrial wastewater; at this plant, the air levels of methyl-isobutyl-ketone, chlorobenzene, toluene, and benzene were correlated significantly with the concentration of total organic vapors in the air. Significant correlations between waste water and air space were established only for the concentrations of trichloroethylene, 1,1,1-trichloroethane and perchloroethylene; no such correlations were encountered for the concentrations of total aliphatic and nonaliphatic hydrocarbons or for total specific compounds. Comparison between the time weighted averages of 24 organics in the air obtained with the charcoal tubes and analyzed by gas chromatography and those obtained with the flame ionization detector and organic vapor analyzer system revealed that the total organics calculated according to the former method amounted to less than 10 percent of the time weighted average results from the flame ionization detector and organic vapor analyzer system.
 
发 布 者:  admin 添 加 时 间:  2007/7/3 点 击 数: 841
 
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