溫石(shi)棉塊體通常為(wei)不同色調的綠色及黃色,也有(you)的為(wei)白色。劈分后的絲狀纖維(wei)為(wei)白色,絲絹(juan)光澤;硬度2~2.5;理論密(mi)度為(wei)2.56g/cm3,化學成(cheng)分中類質同象代替,決(jue)定實(shi)際密(mi)度值(zhi)的大小(xiao)(xiao),Fe、Ti、Mn、Ni等元素取(qu)(qu)代Mg時(shi),密(mi)度偏(pian)大,Al、Ti取(qu)(qu)代Si時(shi),密(mi)度偏(pian)小(xiao)(xiao),與纖維(wei)管(guan)心有(you)無充(chong)填物也有(you)關系,實(shi)際密(mi)度為(wei)2.426~2.646 g/cm3。
溫石棉的光學性質
溫(wen)石棉的(de)光學性(xing)質,折射率Ng為1.534~1.555,Np為1.522~1.549,Ng值隨(sui)Fe2O3及(ji)(ji)FeO含量增(zeng)多而(er)增(zeng)大(da),Np值隨(sui)FeO及(ji)(ji)H2O+含量增(zeng)多而(er)增(zeng)大(da);多色(se)性(xing),Ng為各(ge)種色(se)調的(de)綠色(se),Np為各(ge)種色(se)調的(de)黃色(se);平行消(xiao)光,正延性(xing)為主。
衍射特征
溫石(shi)(shi)棉的X射(she)(she)線衍(yan)(yan)射(she)(she)特征,有兩條強衍(yan)(yan)射(she)(she)線,d(002)為0.728~0.740nm和d(004)為0.369~0.366nm;另有四(si)條中強衍(yan)(yan)射(she)(she)線,d(020)為0.437~0.459nm、d(201)為0.256~0.260nm、d(202)為0.243~0.248nm、d(402)為0.130~0.134nm。溫石(shi)(shi)棉在自然界產(chan)出以2Mc型纖蛇紋石(shi)(shi)最(zui)多,ZORc型正纖蛇紋石(shi)(shi)少見。
溫石棉的熱效應
溫石棉的(de)熱(re)效(xiao)應,在670~730℃區間出現深(shen)而大(da)的(de)放(fang)熱(re)效(xiao)應(吸熱(re)谷或脫羥(qian)谷);815~830℃區間出現矮而窄(zhai)的(de)放(fang)熱(re)效(xiao)應(熱(re)放(fang)峰),原礦物結(jie)構被徹底(di)破壞,形成(cheng)新(xin)的(de)物相,即鎂橄欖(lan)石和頑(wan)輝石的(de)混合(he)相。
溫石棉的(de)紅外光(guang)譜
溫石棉的紅(hong)外光譜,不同結(jie)晶程(cheng)度的溫石棉,主要表現在1100~950cm-1三個方向的Si—O伸縮(suo)振動帶及3700~3600cm-1羥(qian)基吸收振動的差別。
溫石棉的電子(zi)顯微像多為(wei)空(kong)心管狀,其(qi)內徑(jing)一般為(wei)6~8nm,外(wai)徑(jing)為(wei)20~50nm。
溫石棉(mian)的理論(lun)化(hua)學成分
SiO2 43.36%、MgO43.64%、H2O+13%。一般(ban)含有(you)Fe2O3、FeO、TiO2、Al2O3、MnO、CaO、K2O、Na2O、Cr2O3、V2O5、NiO、F-、Cl等(deng)雜質。表明(ming)混有(you)磁鐵礦(kuang)、方解石(shi)、白(bai)云石(shi)、菱(ling)鎂礦(kuang)、水(shui)(shui)滑石(shi)、石(shi)英、水(shui)(shui)鎂石(shi)、鉻尖晶石(shi)等(deng)雜質礦(kuang)物或元素的類質同象取代。
溫石(shi)棉具有多種物理化學性質,劈分(fen)性能優良(liang),能最(zui)大限度地(di)劈分(fen)為絲狀體,劈分(fen)直徑最(zui)小為1~2μm。工業利用以(yi)比(bi)表(biao)面積為衡(heng)量(liang)指標,一般在5~50m2/g。機械強度高(gao),抗張強度值為120~350(單位(wei)9.8×106Pa)。
其中:高強度(du)(du)纖(xian)維(wei)大于(yu)350,正常強度(du)(du)纖(xian)維(wei)小于(yu)350、大于(yu)250,中等強度(du)(du)纖(xian)維(wei)小于(yu)250、大于(yu)150,低強度(du)(du)纖(xian)維(wei)小于(yu)150。溫(wen)石(shi)棉(mian)(mian)纖(xian)維(wei)強度(du)(du)優于(yu)角(jiao)閃(shan)石(shi)類石(shi)棉(mian)(mian)及人造碳纖(xian)維(wei),與硼纖(xian)維(wei)和(he)玻(bo)璃纖(xian)維(wei)接近。耐熱性(xing)能(neng)(neng)(neng)良好(hao),工業利用溫(wen)度(du)(du)可(ke)達500℃(熱失重率(lv)(lv)小于(yu)1%)。溫(wen)石(shi)棉(mian)(mian)耐堿腐蝕性(xing)強,堿蝕量為(wei)0.46%~0.74%,耐酸腐蝕性(xing)差(cha),不如角(jiao)閃(shan)石(shi)石(shi)棉(mian)(mian),酸蝕量一般(ban)(ban)為(wei)55%~58%。隔熱性(xing)能(neng)(neng)(neng)和(he)導熱性(xing)能(neng)(neng)(neng)好(hao),導熱系數(shu)一般(ban)(ban)為(wei)0.121~0.227W/(m·K)。電絕緣性(xing)良好(hao),電阻率(lv)(lv)ρ一般(ban)(ban)為(wei)0.6×108~4×108Ω·cm。
溫(wen)石棉(mian)纖維(wei)還(huan)具有過濾性[透過系數為(wei)(wei)15%~60%,阻力(li)為(wei)(wei)0.4×9.8~13.9×9.8Pa]、成膜打漿性、磁(ci)性(雙(shuang)磁(ci)化系數為(wei)(wei)6×10^-6~10×10^-6cm/g)、電(dian)動電(dian)位(一般(ban)e>20mV)等。
石(shi)(shi)(shi)棉(mian)(mian)有致癌性(xing)早(zao)已為相(xiang)關行業周知,但石(shi)(shi)(shi)棉(mian)(mian)細分為溫(wen)(wen)(wen)石(shi)(shi)(shi)棉(mian)(mian)和閃石(shi)(shi)(shi)棉(mian)(mian)。經(jing)中(zhong)外多(duo)位礦物(wu)學、病理(li)(li)學、毒性(xing)學專(zhuan)家(jia)學者在(zai)長達2年(nian)多(duo)的(de)比較試驗證明,在(zai)溫(wen)(wen)(wen)石(shi)(shi)(shi)棉(mian)(mian)、閃石(shi)(shi)(shi)棉(mian)(mian)及其他(ta)多(duo)種(zhong)“溫(wen)(wen)(wen)石(shi)(shi)(shi)棉(mian)(mian)替代纖(xian)維”中(zhong),溫(wen)(wen)(wen)石(shi)(shi)(shi)棉(mian)(mian)是相(xiang)對最安(an)全(quan)的(de)無機纖(xian)維材料。自從2004年(nian),瑞士著(zhu)名的(de)吸入(ru)毒物(wu)專(zhuan)家(jia)、多(duo)國政府毒物(wu)學顧問大(da)衛·伯恩(en)斯坦(tan)博士公布“溫(wen)(wen)(wen)石(shi)(shi)(shi)棉(mian)(mian)可以安(an)全(quan)使用(yong)”的(de)實(shi)驗結(jie)果之(zhi)后,2年(nian)來,中(zhong)國、俄羅斯、加拿大(da)、印度、巴西、墨西哥(ge)等國多(duo)位礦物(wu)學、病理(li)(li)學、毒性(xing)學專(zhuan)家(jia),經(jing)過各(ge)自的(de)科學實(shi)驗,得(de)出與伯恩(en)斯坦(tan)博士完全(quan)一致的(de)結(jie)論。
然而(er),2001年三月WTO做(zuo)出具有里程碑意義的裁(cai)定(ding),認(ren)(ren)為溫石(shi)棉(mian)(mian)既然已被認(ren)(ren)定(ding)是(shi)致癌(ai)物質,石(shi)棉(mian)(mian)生產商堅持的安全使(shi)用極限就不存(cun)在。使(shi)得WTO的各個成員國禁(jin)止(zhi)使(shi)用或進(jin)口(kou)如石(shi)棉(mian)(mian)等含致癌(ai)物質的權利合法化,也(ye)進(jin)一(yi)步確認(ren)(ren)WTO各成員國有權認(ren)(ren)為保護生命和健康比履行貿易(yi)義務更為重要。
石棉(mian)的(de)致(zhi)癌性早已(yi)被學界(jie)所(suo)知,但國內行業,特別是建筑行業并沒有禁(jin)用,政府雖(sui)然(ran)規定了開采加工溫石棉(mian)必須佩戴防護(hu)用品,但對于應(ying)用并沒有給出(chu)相(xiang)應(ying)規范和引導。
石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)分為蛇紋石(shi)(shi)(shi)(shi)(shi)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(溫(wen)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian))和角閃(shan)石(shi)(shi)(shi)(shi)(shi)類石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(青石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)、陽(yang)起石(shi)(shi)(shi)(shi)(shi)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)、直閃(shan)石(shi)(shi)(shi)(shi)(shi)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)、鐵石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)、透閃(shan)石(shi)(shi)(shi)(shi)(shi)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian))兩(liang)類。中國(guo)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)資源絕大部分為溫(wen)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)礦(kuang),溫(wen)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian) 占(zhan)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)總產(chan)量的95%以上(shang)。石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)使(shi)用的安全(quan)性(xing)是(shi)(shi)(shi)礦(kuang)物工業(ye)產(chan)業(ye)一個具有(you)爭議性(xing)的話題。石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)所(suo)致(zhi)職業(ye)病中對(dui)人體危害(hai)最(zui)嚴(yan)重(zhong)的是(shi)(shi)(shi)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)肺(fei)(fei)、肺(fei)(fei)癌以及(ji)間皮瘤(liu)。在(zai)所(suo)有(you)種(zhong)類石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)中,致(zhi)病能(neng)力最(zui)強的是(shi)(shi)(shi)青石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian),對(dui)于(yu)溫(wen)石(shi)(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)潛在(zai)致(zhi)癌、致(zhi)纖維化的能(neng)力還存在(zai)爭議。
溫石(shi)棉(mian)的(de)致癌和(he)致纖維化機(ji)制
溫(wen)石(shi)(shi)棉(mian)同其(qi)他種類(lei)石(shi)(shi)棉(mian)的(de)(de)致(zhi)病機(ji)(ji)(ji)制大(da)致(zhi)相同,其(qi)危害來自加工時產生的(de)(de)粉(fen)塵纖(xian)(xian)(xian)維(wei)。這(zhe)些細(xi)小(xiao)的(de)(de)纖(xian)(xian)(xian)維(wei)通過呼(hu)(hu)吸進入(ru)肺(fei)內(nei),大(da)部(bu)分(fen)經呼(hu)(hu)吸道的(de)(de)廓清(qing)體(ti)系(黏(nian)液纖(xian)(xian)(xian)毛廓清(qing)機(ji)(ji)(ji)制和有效的(de)(de)咳(ke)嗽)排(pai)(pai)出(chu)體(ti)外,如果不能排(pai)(pai)出(chu),可(ke)被肺(fei)泡巨噬(shi)細(xi)胞(bao)(bao)所(suo)吞噬(shi)或穿透(tou)上(shang)皮細(xi)胞(bao)(bao)而進入(ru)肺(fei)間(jian)質,從而在體(ti)內(nei)持(chi)續停留很長時間(jian)。滯留的(de)(de)溫(wen)石(shi)(shi)棉(mian)纖(xian)(xian)(xian)維(wei)引發炎癥反應和氧化應激反應,這(zhe)是石(shi)(shi)棉(mian)致(zhi)細(xi)胞(bao)(bao)損(sun)傷的(de)(de)重要(yao)機(ji)(ji)(ji)制。目前溫(wen)石(shi)(shi)棉(mian)致(zhi)纖(xian)(xian)(xian)維(wei)化和致(zhi)癌的(de)(de)機(ji)(ji)(ji)制仍未充分(fen)闡明(ming),主要(yao)認為包含以下機(ji)(ji)(ji)制:
1)機械損傷:溫石棉多數以元纖維(wei)的形態侵入人(ren)體,這類纖維(wei)為結晶態,銳利并(bing)有尖刺,可(ke)以刺破肺泡上(shang)皮細胞和(he)胸膜間皮細胞,對染色體和(he)DNA造(zao)成機械干擾和(he)損傷,導致肺癌和(he)間皮瘤發生。
2)自(zi)(zi)由(you)(you)基和(he)細(xi)胞(bao)(bao)(bao)因子(zi)介導(dao)(dao)的損(sun)(sun)傷(shang):溫(wen)石(shi)(shi)棉(mian)纖(xian)(xian)(xian)維(wei)基于自(zi)(zi)身的化(hua)學特(te)性(xing)(xing)和(he)通過(guo)(guo)激活(huo)肺泡巨噬(shi)細(xi)胞(bao)(bao)(bao),可以誘(you)導(dao)(dao)過(guo)(guo)氧化(hua)氫(qing)、超氧化(hua)物陰離子(zi)和(he)氫(qing)氧根離子(zi)等(deng)活(huo)性(xing)(xing)氧的產生,導(dao)(dao)致DNA損(sun)(sun)傷(shang)和(he)纖(xian)(xian)(xian)維(wei)化(hua)。一方面(mian)(mian)溫(wen)石(shi)(shi)棉(mian)纖(xian)(xian)(xian)維(wei)表面(mian)(mian)存在的不飽和(he)O-Si-O、Si-O-Si和(he)Mg-O鍵等(deng),具(ju)有(you)很強的表面(mian)(mian)活(huo)性(xing)(xing),含氧自(zi)(zi)由(you)(you)基引(yin)(yin)起細(xi)胞(bao)(bao)(bao)膜(mo)(mo)自(zi)(zi)由(you)(you)基的鏈(lian)(lian)式(shi)反應(ying);另一方面(mian)(mian)溫(wen)石(shi)(shi)棉(mian)還可通過(guo)(guo)刺激巨噬(shi)細(xi)胞(bao)(bao)(bao)發(fa)生呼吸(xi)爆發(fa)及崩解死亡,釋放一系列(lie)溶酶體(ti)酶、炎(yan)性(xing)(xing)細(xi)胞(bao)(bao)(bao)因子(zi)及活(huo)性(xing)(xing)氧自(zi)(zi)由(you)(you)基。在兩種機(ji)制作(zuo)用下,細(xi)胞(bao)(bao)(bao)膜(mo)(mo)上多聚不飽和(he)脂肪酸(suan)發(fa)生脂質(zhi)過(guo)(guo)氧化(hua)反應(ying),引(yin)(yin)起細(xi)胞(bao)(bao)(bao)和(he)基質(zhi)損(sun)(sun)傷(shang)。溫(wen)石(shi)(shi)棉(mian)纖(xian)(xian)(xian)維(wei)通過(guo)(guo)對巨噬(shi)細(xi)胞(bao)(bao)(bao)和(he)成(cheng)纖(xian)(xian)(xian)維(wei)細(xi)胞(bao)(bao)(bao)的細(xi)胞(bao)(bao)(bao)膜(mo)(mo)的脂質(zhi)過(guo)(guo)氧化(hua)作(zuo)用,引(yin)(yin)起細(xi)胞(bao)(bao)(bao)和(he)基質(zhi)成(cheng)分(fen)損(sun)(sun)傷(shang),促進成(cheng)纖(xian)(xian)(xian)維(wei)細(xi)胞(bao)(bao)(bao)增(zeng)殖和(he) 膠原(yuan)合成(cheng),導(dao)(dao)致整個肺泡結構單(dan)位(wei)(wei)破壞(huai),形成(cheng)不可逆(ni)的纖(xian)(xian)(xian)維(wei)化(hua),即石(shi)(shi)棉(mian)肺等(deng)肺部(bu)纖(xian)(xian)(xian)維(wei)化(hua)疾病(bing)。溫(wen)石(shi)(shi)棉(mian)纖(xian)(xian)(xian)維(wei)所致遺(yi)傳毒性(xing)(xing)早期改(gai)(gai)變(bian)(bian)(bian)主(zhu)要(yao)通過(guo)(guo)DNA損(sun)(sun)傷(shang)和(he)染色(se)體(ti)改(gai)(gai)變(bian)(bian)(bian)途(tu)徑(jing)(jing)。在DNA層(ceng)面(mian)(mian),主(zhu)要(yao)通過(guo)(guo)DNA單(dan)鏈(lian)(lian)、雙鏈(lian)(lian)斷(duan)(duan)裂(lie)、氧化(hua)損(sun)(sun)傷(shang)等(deng)途(tu)徑(jing)(jing)引(yin)(yin)起細(xi)胞(bao)(bao)(bao)致突變(bian)(bian)(bian)性(xing)(xing)。在染色(se)體(ti)層(ceng)面(mian)(mian),主(zhu)要(yao)通過(guo)(guo)使染色(se)體(ti)或染色(se)體(ti)單(dan)體(ti)發(fa)生斷(duan)(duan)裂(lie)、缺失(shi)、 倒位(wei)(wei)以及姐妹染色(se)體(ti)單(dan)體(ti)互換(huan)等(deng),引(yin)(yin)起染色(se)體(ti)畸變(bian)(bian)(bian)或數目改(gai)(gai)變(bian)(bian)(bian),從而產生致突變(bian)(bian)(bian)作(zuo)用。
3)原(yuan)癌(ai)基(ji)因(yin)(yin)(yin)激活(huo)和(he)抑癌(ai)基(ji)因(yin)(yin)(yin)失活(huo):溫石(shi)棉可以改變細(xi)胞信號傳導系(xi)統,激活(huo)原(yuan)癌(ai)基(ji)因(yin)(yin)(yin)并(bing)導致抑癌(ai)基(ji)因(yin)(yin)(yin)失活(huo),進而影響細(xi)胞的增殖和(he)分化,引起肺(fei)癌(ai)和(he)間(jian)皮瘤的發(fa)生。
溫石棉致(zhi)病性的影響因素
濃(nong)度對溫石棉(mian)致病性的影響
國(guo)內外研(yan)(yan)究(jiu)認為(wei)作業環境(jing)空氣(qi)中溫石棉粉塵質量(liang)濃度(du)(du)(du)(以(yi)下簡稱濃度(du)(du)(du))與石棉肺(fei)發病有明顯的(de)(de)(de)劑量(liang)反應(ying)(ying)(ying)關系,它在(zai)空氣(qi)中的(de)(de)(de)含(han)量(liang)必(bi)須達(da)到(dao)一定程度(du)(du)(du),才(cai)會對(dui)人(ren)(ren)體健康造成危害。各研(yan)(yan)究(jiu)分別按(an)1%~3%石棉肺(fei)患病率、30~40年工(gong)作年限(xian)計算,預(yu)測(ce)石棉粉塵容(rong)許濃度(du)(du)(du)應(ying)(ying)(ying)低(di)于(yu)2.71~3.90mg/m3或(huo)石棉纖(xian)維容(rong)許濃度(du)(du)(du)應(ying)(ying)(ying)低(di)于(yu)1.15 ~2.00f/mL(f為(wei)纖(xian)維根數),說明中國(guo)現行工(gong)作場所(suo)石棉粉塵職業接觸(chu)限(xian)值0.8mg/m3或(huo)0.8f/mL是合理的(de)(de)(de),溫石棉纖(xian)維的(de)(de)(de)濃度(du)(du)(du)可以(yi)被控制在(zai)安全(quan)范圍內。同時(shi)也(ye)有學(xue)者(zhe)認為(wei)在(zai)溫石棉接觸(chu)水(shui)平低(di)的(de)(de)(de)人(ren)(ren)群中一直觀(guan)察到(dao)致癌風險的(de)(de)(de)增(zeng)加(jia),因(yin)此溫石棉沒有一定的(de)(de)(de)安全(quan)閾(yu)值。這是部分研(yan)(yan)究(jiu)人(ren)(ren)員認為(wei)溫石棉沒有安全(quan)閾(yu)值的(de)(de)(de)原因(yin)。
形態對溫石棉(mian)致病性(xing)的(de)影響
纖維尺(chi)寸(cun)影響生(sheng)物殘存性,進(jin)而影響肺的(de)呼吸、沉淀和清除(chu)。主要從兩個方(fang)面考慮(lv)尺(chi)寸(cun)的(de)影響:
1)纖維是否(fou)可(ke)吸(xi)入;
2)如(ru)果它處(chu)于(yu)(yu)(yu)(yu)(yu)(yu)可吸(xi)入的(de)尺寸(cun),吸(xi)入肺(fei)(fei)后仍需考慮(lv)纖(xian)維(wei)(wei)(wei)尺寸(cun)的(de)影響。大(da)(da)(da)多數(shu)溫(wen)(wen)石棉(mian)纖(xian)維(wei)(wei)(wei)和粉(fen)(fen)塵(chen)可被(bei)(bei)(bei)氣管(guan)—支氣管(guan)樹的(de)黏(nian)液逐(zhu)步(bu)向上運移并隨咳嗽排出,據病(bing)理學(xue)標本(ben)電鏡(jing)檢(jian)測,肺(fei)(fei)部(bu)沒(mei)有發(fa)現過長(chang)(chang)度大(da)(da)(da)于(yu)(yu)(yu)(yu)(yu)(yu)200μm的(de)纖(xian)維(wei)(wei)(wei),多數(shu)短(duan)(duan)于(yu)(yu)(yu)(yu)(yu)(yu)50μm。進入肺(fei)(fei)部(bu)后,尺寸(cun)很(hen)短(duan)(duan)的(de)纖(xian)維(wei)(wei)(wei),尤(you)其(qi)那些短(duan)(duan)于(yu)(yu)(yu)(yu)(yu)(yu)5μm的(de)纖(xian)維(wei)(wei)(wei)和粉(fen)(fen)塵(chen),能夠被(bei)(bei)(bei)巨(ju)(ju)噬細胞完(wan)全(quan)吞噬,通過類似非纖(xian)維(wei)(wei)(wei)顆粒(li)物(wu)的(de)清(qing)(qing)除(chu)(chu)機制被(bei)(bei)(bei)清(qing)(qing)除(chu)(chu),較(jiao)長(chang)(chang)的(de)纖(xian)維(wei)(wei)(wei)不(bu)能被(bei)(bei)(bei)巨(ju)(ju)噬細胞完(wan)全(quan)吞沒(mei),長(chang)(chang)時間(jian)存(cun)在肺(fei)(fei)內將導致疾病(bing)。而更長(chang)(chang)的(de),長(chang)(chang)于(yu)(yu)(yu)(yu)(yu)(yu)20μm的(de)溫(wen)(wen)石棉(mian)纖(xian)維(wei)(wei)(wei)可以迅速從肺(fei)(fei)部(bu)被(bei)(bei)(bei)清(qing)(qing)除(chu)(chu),不(bu)轉移到胸膜腔,不(bu)啟動纖(xian)維(wei)(wei)(wei)誘發(fa)的(de)反應。特別短(duan)(duan)的(de)可以吞食溶解,比較(jiao)長(chang)(chang)的(de)可被(bei)(bei)(bei)清(qing)(qing)除(chu)(chu),致病(bing)的(de)纖(xian)維(wei)(wei)(wei)集中于(yu)(yu)(yu)(yu)(yu)(yu)中間(jian)長(chang)(chang)度。對人體致癌(ai)危險性(xing)最大(da)(da)(da)的(de)石棉(mian)纖(xian)維(wei)(wei)(wei)是長(chang)(chang)度大(da)(da)(da)于(yu)(yu)(yu)(yu)(yu)(yu)5~8μm、直徑(jing)小于(yu)(yu)(yu)(yu)(yu)(yu)1.5μm或大(da)(da)(da)于(yu)(yu)(yu)(yu)(yu)(yu)0.25μm的(de)纖(xian)維(wei)(wei)(wei)。
除(chu)了長度,纖維形狀也影響其(qi)致病性。角閃石(shi)(shi)(shi)(shi)石(shi)(shi)(shi)(shi)棉(mian)(mian)纖維是鏈(lian)狀結構,而(er)溫石(shi)(shi)(shi)(shi)棉(mian)(mian)纖維是一種褶皺型的(de)或是卷成空心小(xiao)卷的(de)頁硅酸鹽,卷曲的(de)纖維形狀不易于吸入呼(hu)吸道。此外(wai),薄而(er)短的(de)纖維質量更(geng)小(xiao),比厚(hou)而(er)長的(de)纖維在空氣中(zhong)懸浮(fu)的(de)時(shi)(shi)間(jian)更(geng)長。而(er)大多數(shu)的(de)石(shi)(shi)(shi)(shi)棉(mian)(mian)纖維比目前正在開發的(de)新的(de)納米纖維更(geng)厚(hou),說明(ming)其(qi)懸浮(fu)時(shi)(shi)間(jian)更(geng)短,吸入可能(neng)性更(geng)小(xiao)。
可溶性(xing)(xing)與(yu)溫石棉致病性(xing)(xing)的影響(xiang)
在肺(fei)內(nei)沉積時,一(yi)些纖(xian)(xian)(xian)維能夠(gou)直接(jie)完(wan)全溶(rong)解(jie)(jie),另一(yi)些纖(xian)(xian)(xian)維不(bu)能溶(rong)解(jie)(jie),但可(ke)以(yi)(yi)斷裂成(cheng)(cheng)短片(pian)后(hou)被成(cheng)(cheng)功吞(tun)噬(shi)和清除(chu)。可(ke)溶(rong)性(xing)高(gao)的(de)纖(xian)(xian)(xian)維表現較(jiao)低(di)(di)的(de)致病(bing)性(xing),而可(ke)溶(rong)性(xing)不(bu)佳的(de)纖(xian)(xian)(xian)維致病(bing)性(xing)較(jiao)強。溫(wen)石(shi)棉(mian)(mian)可(ke)以(yi)(yi)被強酸(比如巨(ju)噬(shi)細(xi)胞吞(tun)噬(shi)時產生的(de)酸)分解(jie)(jie),有更好的(de)可(ke)溶(rong)解(jie)(jie)性(xing)以(yi)(yi)及(ji)更小(xiao)的(de)生物殘存性(xing),這(zhe)(zhe)將(jiang)減(jian)低(di)(di)其對身體的(de)致病(bing)性(xing)。而角(jiao)閃石(shi)類石(shi)棉(mian)(mian)更頑固,在多數(shu)情況下都不(bu)會被破壞,因此(ci)有較(jiao)強的(de)致癌性(xing)。溫(wen)石(shi)棉(mian)(mian)是一(yi)種(zhong)片(pian)狀硅酸鹽,呈薄層而卷曲(qu)的(de)形態(tai),約0.8nm厚(hou),是由鎂和二氧化硅組成(cheng)(cheng)的(de)夾層結構。肺(fei) 巨(ju)噬(shi)細(xi)胞提供的(de)酸性(xing)環(huan)境可(ke)以(yi)(yi)快速破壞這(zhe)(zhe)種(zhong)片(pian)狀結構,將(jiang)溫(wen)石(shi)棉(mian)(mian)纖(xian)(xian)(xian)維分解(jie)(jie)成(cheng)(cheng)小(xiao)片(pian),隨后(hou)這(zhe)(zhe)些碎片(pian)可(ke)以(yi)(yi)很容易地從肺(fei)部清除(chu)。
角(jiao)閃石類(lei)石棉是(shi)實(shi)心棒狀(zhuang)雙鏈的(de)四(si)面體硅酸鹽纖維,這(zhe)使得它非常結實(shi)耐(nai)(nai)用。角(jiao)閃石類(lei)石棉晶體結構的(de)外表面像石英一樣,并且具有(you)類(lei)似石英的(de)耐(nai)(nai)化學性。角(jiao)閃石類(lei)石棉纖維在任何pH值下都(dou)不(bu)會溶(rong)解。
吸煙對(dui)溫石(shi)棉致病(bing)性的(de)影響
煙(yan)(yan)草和(he)石(shi)棉(mian)(mian)都是國際抗癌(ai)聯盟(IARC)宣(xuan)布的(de)人類致癌(ai)物,吸(xi)(xi)煙(yan)(yan)會對溫(wen)(wen)石(shi)棉(mian)(mian)接觸者(zhe)肺癌(ai)的(de)發生起協同(tong)(tong)作用(yong)。吸(xi)(xi)煙(yan)(yan)降低(di)機體清除溫(wen)(wen)石(shi)棉(mian)(mian)纖(xian)維和(he)粉塵的(de)功能,使(shi)石(shi)棉(mian)(mian)塵易(yi)沉(chen)積于(yu)呼(hu)吸(xi)(xi)系統中,同(tong)(tong)時(shi)煙(yan)(yan)溶(rong)液(ye)抑制了巨噬(shi)細(xi)胞(bao)的(de)吞噬(shi)功能,使(shi)巨噬(shi)細(xi)胞(bao)不能有效地(di)防(fang)御侵襲,從而使(shi)溫(wen)(wen)石(shi)棉(mian)(mian)直(zhi)接作用(yong)于(yu)靶(ba)細(xi)胞(bao),加劇自由(you)基的(de)生成(cheng),進(jin)而導致DNA損傷(shang),產生更為(wei)嚴重的(de)損害。有調查(cha)表明(ming),不接觸溫(wen)(wen)石(shi)棉(mian)(mian)的(de)吸(xi)(xi)煙(yan)(yan)者(zhe)肺癌(ai)相對危險度(RR)為(wei)26,不吸(xi)(xi)煙(yan)(yan)的(de)溫(wen)(wen)石(shi)棉(mian)(mian)接觸者(zhe)肺癌(ai)RR為(wei)12.2,而接觸溫(wen)(wen)石(shi)棉(mian)(mian)的(de)吸(xi)(xi)煙(yan)(yan)者(zhe)肺癌(ai)RR高達32.1,吸(xi)(xi)煙(yan)(yan)和(he)溫(wen)(wen)石(shi)棉(mian)(mian)接觸協同(tong)(tong)指數(shu)為(wei)2.2。
降低溫石棉致病性(xing)的研究
有研究(jiu)(jiu)發現經檸檬酸鋁、混合稀土(tu)或亞(ya)硒酸鈉3種化合物預(yu)處理(li)的(de)溫(wen)(wen)(wen)石(shi)棉(mian)纖維表面(mian)元素的(de)構(gou)成和含(han)量均發生變(bian)化,導(dao)致相比未預(yu)處理(li)的(de)溫(wen)(wen)(wen)石(shi)棉(mian),該類溫(wen)(wen)(wen)石(shi)棉(mian)作用于細(xi)(xi)胞(bao)時,細(xi)(xi)胞(bao)的(de)酸性(xing)磷酸酶活(huo)性(xing)降低,人胚肺細(xi)(xi)胞(bao)存活(huo)率提(ti)高(gao)及超微結構(gou)改變(bian),癌基(ji)因轉錄水平降低,最(zui)終減輕了溫(wen)(wen)(wen)石(shi)棉(mian)的(de)細(xi)(xi)胞(bao)毒(du)性(xing)。另有研究(jiu)(jiu)發現大蒜(suan)提(ti)取物能有效減少溫(wen)(wen)(wen)石(shi)棉(mian)對外周血(xue)淋巴細(xi)(xi)胞(bao)的(de)基(ji)因毒(du)性(xing)。
溫石棉所致職業性腫(zhong)瘤(liu)流行病學研(yan)究
國(guo)內(nei)大量流行病(bing)學調(diao)查(cha)研究(jiu)提示溫石(shi)棉粉(fen)塵在接觸濃度(du)超標條件下具有顯(xian)著的(de)致病(bing)性(xing)。
對重慶石(shi)(shi)(shi)棉(mian)(mian)廠接觸(chu)純溫石(shi)(shi)(shi)棉(mian)(mian)工人的(de)25年縱向(xiang)隊列研(yan)究顯示,生料間和紡織間的(de)粉塵(chen)(chen)(chen)濃度(du)(du)分別(bie)為(wei)7.6f/mL和4.5f/mL,接塵(chen)(chen)(chen)組的(de)肺癌發病率(lv)是不接塵(chen)(chen)(chen)組的(de)8.1倍(bei)。對中國另一(yi)大型(xing)石(shi)(shi)(shi)棉(mian)(mian)廠515名單純接觸(chu)溫石(shi)(shi)(shi)棉(mian)(mian)的(de)工人進(jin)行27年的(de)追蹤研(yan)究發現,其20世紀(ji)60年代前溫石(shi)(shi)(shi)棉(mian)(mian)粉塵(chen)(chen)(chen)平(ping)均濃度(du)(du)為(wei)146.2mg/m3,20世紀(ji)90年代后降低到10mg/m3,單純接觸(chu)溫石(shi)(shi)(shi)棉(mian)(mian)工人的(de)肺癌發生率(lv)顯著(zhu)超高(P<0.05)。
另有長達41年(nian)(nian)調查浙江家(jia)庭(ting)溫(wen)(wen)石(shi)棉手工(gong)紡織業(ye)的(de)研(yan)(yan)究(jiu)(jiu)發現(xian),其(qi)20世(shi)紀(ji)60年(nian)(nian)代作業(ye)環(huan)境的(de)溫(wen)(wen)石(shi)棉粉塵濃度(du)(du)38.00~73.00mg/m3,20世(shi)紀(ji)70年(nian)(nian)代降低到平(ping)均為1.25 mg/m3,但仍(reng)超標(biao),作業(ye)女工(gong)5681人中累計死(si)(si)亡858例(li),其(qi)中213人死(si)(si)于(yu)(yu)癌(ai)癥(zheng),肺(fei)(fei)癌(ai)居(ju)首位(wei)(87例(li),占40.85%),肺(fei)(fei)癌(ai)標(biao)準(zhun)化(hua)死(si)(si)亡比3.88,明(ming)(ming)顯高(gao)于(yu)(yu)當地女性年(nian)(nian)齡(ling)別標(biao)準(zhun)化(hua)死(si)(si)亡比。對某大型溫(wen)(wen)石(shi)棉礦(kuang)研(yan)(yan)究(jiu)(jiu)發現(xian),接觸溫(wen)(wen)石(shi)棉可以提高(gao)礦(kuang)工(gong)肺(fei)(fei)癌(ai)、石(shi)棉肺(fei)(fei)等(deng)疾(ji)病的(de)死(si)(si)亡率。而(er)國(guo)外研(yan)(yan)究(jiu)(jiu)認為,低于(yu)(yu)限值濃度(du)(du)的(de)溫(wen)(wen)石(shi)棉纖(xian)維粉塵不會造成(cheng)健康風險。毒理學博士David Bernstein的(de)研(yan)(yan)究(jiu)(jiu)表明(ming)(ming),溫(wen)(wen)石(shi)棉和角閃(shan)石(shi)在(zai)動力和病理上都存在(zai)差異,其(qi)他類似研(yan)(yan)究(jiu)(jiu)也(ye)展示(shi)出對溫(wen)(wen)石(shi)棉的(de)低程度(du)(du)接觸不會導致可被(bei)檢測的(de)安全(quan)風險。
有證據表明,高濃(nong)度(du)和長時(shi)間(jian)接(jie)(jie)(jie)(jie)觸溫(wen)石(shi)棉(mian)(mian)(mian)(mian)可(ke)以(yi)產生肺(fei)癌,低濃(nong)度(du)溫(wen)石(shi)棉(mian)(mian)(mian)(mian)不存在(zai)可(ke)檢測的健(jian)(jian)康風險,即(ji)使短時(shi)間(jian)接(jie)(jie)(jie)(jie)觸高濃(nong)度(du)溫(wen)石(shi)棉(mian)(mian)(mian)(mian),發(fa)生健(jian)(jian)康風險的概率(lv)也不高。希臘持續39年的關(guan)于接(jie)(jie)(jie)(jie)觸純(chun)溫(wen)石(shi)棉(mian)(mian)(mian)(mian)的水泥工人的研(yan)(yan)究表明,對純(chun)凈溫(wen)石(shi)棉(mian)(mian)(mian)(mian)在(zai)允許范圍內的職業接(jie)(jie)(jie)(jie)觸與肺(fei)癌以(yi)及間(jian)皮瘤的顯著增長無關(guan)。而有巴西的研(yan)(yan)究發(fa)現,減少石(shi)棉(mian)(mian)(mian)(mian)接(jie)(jie)(jie)(jie) 觸可(ke)以(yi)顯著降(jiang)低石(shi)棉(mian)(mian)(mian)(mian)肺(fei)、實質和/或良性胸膜疾病(bing)的發(fa)病(bing)率(lv)。
溫石棉同角(jiao)閃石類石棉致病性差(cha)異的流行病
溫(wen)石(shi)(shi)棉和(he)角(jiao)(jiao)閃石(shi)(shi)石(shi)(shi)棉在吸入毒性和(he)致病(bing)性上存(cun)在差(cha)異。David Bernstein認(ren)為,在化學特(te)性和(he)礦物(wu)學特(te)性方面,溫(wen)石(shi)(shi)棉與其他角(jiao)(jiao)閃石(shi)(shi)石(shi)(shi)棉差(cha)異明(ming)顯,可以從肺中更(geng)快速地被清除(chu)。
6個中歐(ou)、東歐(ou)國家和(he)(he)英國的(de)(de)(de)(de)多中心(xin)對(dui)照研(yan)究(jiu)發現,職業接觸石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)似乎并不(bu)促進(jin)男性肺(fei)癌的(de)(de)(de)(de)發病,溫(wen)(wen)(wen)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)誘(you)發肺(fei)癌的(de)(de)(de)(de)概率(lv)小于溫(wen)(wen)(wen)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)合并角(jiao)閃石(shi)(shi)(shi)(shi)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)。另有研(yan)究(jiu)計數(shu)133名間皮(pi)瘤(liu)患者(zhe)和(he)(he)262名肺(fei)癌患者(zhe)的(de)(de)(de)(de)肺(fei)組(zu)織標(biao)本中長度超過5μm的(de)(de)(de)(de)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)纖維(wei)數(shu)目,發現溫(wen)(wen)(wen)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)纖維(wei)僅占2%。英國健康(kang)安全(quan)理事(shi)會(hui)的(de)(de)(de)(de)研(yan)究(jiu)表明溫(wen)(wen)(wen)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)和(he)(he)其(qi)他(ta)兩類角(jiao)閃石(shi)(shi)(shi)(shi)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)在間皮(pi)瘤(liu)風險上的(de)(de)(de)(de)差異為1∶100∶500。總(zong)結71個石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)群體的(de)(de)(de)(de)廣泛(fan)的(de)(de)(de)(de)流(liu)行(xing)病學研(yan)究(jiu)表明,沒有任何證(zheng)據(ju)支持未被角(jiao)閃石(shi)(shi)(shi)(shi)污染的(de)(de)(de)(de)溫(wen)(wen)(wen)石(shi)(shi)(shi)(shi)棉(mian)(mian)(mian)(mian)(mian)會(hui)導致間皮(pi)瘤(liu)的(de)(de)(de)(de)這種(zhong)假設(she)。
溫石棉致病機制的研究方向及展(zhan)望
溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)致(zhi)(zhi)(zhi)癌和(he)致(zhi)(zhi)(zhi)纖(xian)(xian)維(wei)(wei)(wei)化的(de)(de)(de)機制(zhi)十分復(fu)雜,至今仍存(cun)在很多尚未研(yan)究清楚之處。比如溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)在細(xi)胞(bao)信號傳導層面的(de)(de)(de)完(wan)整致(zhi)(zhi)(zhi)病(bing)機制(zhi)如何;不(bu)同產(chan)地(di)的(de)(de)(de)溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)成分有所(suo)不(bu)同,對溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)的(de)(de)(de)致(zhi)(zhi)(zhi)病(bing)性(xing)影響如何;溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)同時具有致(zhi)(zhi)(zhi)癌性(xing)和(he)致(zhi)(zhi)(zhi)纖(xian)(xian)維(wei)(wei)(wei)化性(xing),溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)有哪些較其他致(zhi)(zhi)(zhi)癌物或致(zhi)(zhi)(zhi)纖(xian)(xian)維(wei)(wei)(wei)化物質不(bu)同之處;在細(xi)胞(bao)層面,溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)和(he)其他種類(lei)石(shi)棉(mian)(mian)(mian)(mian)的(de)(de)(de)致(zhi)(zhi)(zhi)病(bing)機制(zhi)存(cun)在哪些區(qu)別;是否(fou)存(cun)在有效降低溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)致(zhi)(zhi)(zhi)病(bing)性(xing)的(de)(de)(de)方(fang)(fang)法及其應用等。對溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)致(zhi)(zhi)(zhi)病(bing)機制(zhi)、影響因素(su)及降低毒(du)性(xing)方(fang)(fang)法的(de)(de)(de)完(wan)整研(yan)究,可以幫助(zhu)人們更(geng)全面地(di)認識溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)的(de)(de)(de)危(wei)害,并在此基礎(chu)上研(yan)發適宜的(de)(de)(de)防護措(cuo)施(shi)和(he)防護手段,以更(geng)安全、健(jian)康地(di)應用溫(wen)(wen)(wen)石(shi)棉(mian)(mian)(mian)(mian)。