溫州市PM2.5中水溶性離子污染特征及來源分析

葛琳琳，鄭元鑄，涂圣鋒，朱京科，王俏麗，王向前，李素靜*，李 偉,

(1.浙江大學(xué) 環(huán)境工程研究所，浙江 杭州 310058； 2.溫州市環(huán)境監(jiān)測(cè)中心站 浙江 溫州 325003； 3.浙江大學(xué) 生物質(zhì)

溫州市PM2.5中水溶性離子污染特征及來源分析

葛琳琳1，鄭元鑄2，涂圣鋒2，朱京科3，王俏麗4，王向前3，李素靜3*，李 偉1,3

(1.浙江大學(xué) 環(huán)境工程研究所，浙江 杭州 310058； 2.溫州市環(huán)境監(jiān)測(cè)中心站 浙江 溫州 325003； 3.浙江大學(xué) 生物質(zhì)

化工教育部重點(diǎn)實(shí)驗(yàn)室 工業(yè)生態(tài)與環(huán)境研究所，浙江 杭州 310027； 4.浙江大學(xué) 熱能工程研究所，浙江 杭州 310027)

溫州；PM2.5；水溶性離子；污染特征；源解析

Characteristics and sources apportionment of water-soluble ions in PM2.5of Wenzhou, Zhejiang Province. Journal of Zhejiang University(Science Edition), 2017,44(1):112-119

0 引 言

溫州市位于浙江省東南沿海地區(qū)，產(chǎn)業(yè)特色為服裝、電器、制鞋、制革、汽摩配和印刷包裝等，是浙江省經(jīng)濟(jì)發(fā)展較快的城市之一.隨著城市化進(jìn)程的加快以及工業(yè)的迅速發(fā)展，灰霾、酸雨和光化學(xué)污染等大氣污染問題日益凸顯，亦越來越受關(guān)注.據(jù)溫州市2014年環(huán)境狀況公報(bào)，其大氣首要超標(biāo)污染物為PM2.5，全市平均霾日數(shù)為62.5 d，比2013年減少33%(30 d).目前，還沒有關(guān)于溫州市大氣PM2.5中水溶性離子的研究.為此，本研究在溫州城區(qū)設(shè)置4個(gè)采樣點(diǎn)，分4個(gè)季度采集PM2.5樣品，研究溫州市大氣PM2.5中水溶性離子的污染特征和主要來源，對(duì)了解溫州市大氣復(fù)合污染特征、制定有效的防治對(duì)策具有重要意義.

1 材料與方法

1.1 樣品采集

為全面評(píng)價(jià)溫州主城區(qū)(鹿城區(qū)、甌海區(qū)和龍灣區(qū))大氣細(xì)顆粒物的污染現(xiàn)狀，根據(jù)《環(huán)境空氣顆粒物源解析監(jiān)測(cè)技術(shù)方法指南(試行)》(以下簡(jiǎn)稱指南)的規(guī)定，在溫州市區(qū)范圍內(nèi)布設(shè)4個(gè)國控(或省控)監(jiān)測(cè)點(diǎn)位，溫州市環(huán)境監(jiān)測(cè)中心站(簡(jiǎn)稱市站)、溫州市環(huán)境監(jiān)測(cè)中心站甌海分站(簡(jiǎn)稱甌海)、龍灣區(qū)環(huán)境空氣監(jiān)測(cè)點(diǎn)(簡(jiǎn)稱龍灣)以及南浦環(huán)境空氣監(jiān)測(cè)點(diǎn)(簡(jiǎn)稱南浦)進(jìn)行環(huán)境受體樣品采集.4個(gè)采樣點(diǎn)均位于溫州市主城區(qū).市站點(diǎn)位于鹿城區(qū)，南浦和甌海點(diǎn)位于甌海區(qū)，龍灣點(diǎn)位于龍灣區(qū)；市站采樣點(diǎn)位于甌江邊，周圍是學(xué)校和居民區(qū)，大氣污染來源相對(duì)較少；南浦采樣點(diǎn)位于溫州大道和南浦路交匯處，2條道路均是雙向六車道的市區(qū)交通干道，平時(shí)車流量大；甌海附近住宅區(qū)密集，緊鄰交通干道，車流量較大，且附近有一些較大的貨運(yùn)公司；龍灣點(diǎn)位于甌江附近的居民區(qū)，周邊有一些機(jī)械閥門鑄造企業(yè)和混凝土企業(yè).4個(gè)站點(diǎn)同步采集得到的環(huán)境受體樣品能夠代表溫州市區(qū)空氣中PM2.5的來源狀況.具體監(jiān)測(cè)點(diǎn)分布見圖1.

根據(jù)指南中對(duì)采樣時(shí)間及周期的規(guī)定，本項(xiàng)目在充分研究溫州市顆粒物濃度、排放源的季節(jié)性變化特征和氣象因素后，分別于2015年1月4～12日(冬季)、4月16～25日(春季)、7月22～29日(夏季)和10月18～24日(秋季)對(duì)4個(gè)采樣點(diǎn)進(jìn)行同步PM2.5采樣.使用嶗應(yīng)2030型智能TSP中流量采樣器采樣，設(shè)置采樣流量為100 L·min-1.采集的樣品量應(yīng)滿足分析要求且不過載，設(shè)置采樣時(shí)間為20 h.采樣濾膜為石英纖維濾膜(QMA 1851-090型，直徑90 mm).

嶗應(yīng)2030型智能TSP中流量采樣器技術(shù)參數(shù)：

采樣流量：100 L·min-1，分辨率0.1 L·min-1，準(zhǔn)確度≤±5.0%，流量相對(duì)標(biāo)準(zhǔn)偏差≤2.0%；

計(jì)前溫度：-30～99 ℃，分辨率0.1 ℃，準(zhǔn)確度≤±1.0 ℃；

大氣壓：70～130 kPa，分辨率0.01 kPa，準(zhǔn)確度≤±500 Pa；

切割特性：PM10采樣頭Da50=(10±0.5)μm，g≤1.5±0.1；PM2.5采樣頭Da50=(2.5±0.2)μm，g≤1.2±0.1；

入口速度0.3 m·s-1，有效濾膜直徑Φ 80 mm，連接頭M20×1.5，噪聲≤59 dB(A)，工作電源AC220V±10%，50Hz；

圖1 溫州市PM2.5監(jiān)測(cè)點(diǎn)位分布示意Fig.1 Sampling sites of PM2.5 in Wenzhou City

執(zhí)行標(biāo)準(zhǔn):HJ 618-2011《環(huán)境空氣PM10和PM2.5的測(cè)定重量法》,HJ/T 93-2013《環(huán)境空氣顆粒物(PM10和PM2.5)采樣器技術(shù)要求及檢測(cè)方法》.

1.2 膜處理

在樣品采集前，將裝有石英膜的鋁箔袋敞口放到馬弗爐中，在450 ℃條件下灼燒4 h，待石英膜自然冷卻，取出后將鋁箔袋密封.另外，用于保存石英膜膜盒的盒內(nèi)鋁箔也需在450 ℃灼燒4 h，且為避免鑷子直接接觸石英膜，濾膜準(zhǔn)備過程中使用的鑷子需用以上鋁箔包好鑷子尖頭與膜接觸的部分.待樣品采集后，將濾膜放入膜盒密封、編號(hào)，放入-30 ℃的冰箱內(nèi)冷凍保存.采樣前后濾膜均放在恒溫恒濕箱內(nèi)平衡24 h以上，恒重條件設(shè)為溫度(20±1) ℃、相對(duì)濕度(50±5)%RH.平衡后用萬分之一分析天平稱重.

1.3 樣品預(yù)處理及分析

將濾膜剪成約0.5 cm×3 cm的條狀放入帶塞平口試管中，加入20.00 mL超純水，將試管置于超聲儀中超聲震蕩30 min后靜置，取上層清液.上層清液經(jīng)0.22 μm針式過濾頭過濾后，用ICS-1100離子色譜(美國Dionex公司)對(duì)濾液中的水溶性離子進(jìn)行分析.

2 結(jié)果與討論

2.1 PM2.5中水溶性離子濃度

表1 溫州市2015年P(guān)M2.5中主要水溶性離子濃度及占比

表2 不同城市大氣PM2.5中主要水溶性離子濃度

注 BDL表示數(shù)值低于檢測(cè)限.

2.2 PM2.5中水溶性離子時(shí)空變化特征

圖2 2015年觀測(cè)期間溫州市區(qū)PM2.5中水溶性離子的時(shí)空分布Fig.2 Spatial and temporal distribution of water-soluble ions in PM2.5 in Wenzhou during 2015A曲硝酸根硫酸根銨根氯(Cl-) E其他水溶性離子

2.3 陰陽離子平衡

陽離子=

(1)

(2)

圖3 水溶性陰陽離子的相關(guān)性Fig.3 Correlations between anions and cations

溫州市陰離子/陽離子的年均值為1.01±0.11，對(duì)溫州市區(qū)PM2.5中水溶性離子做線性回歸分析，發(fā)現(xiàn)陰陽離子存在明顯相關(guān)性，R2為0.78，平衡方程斜率大于1.由此可見，溫州市區(qū)PM2.5總

2.4 PM2.5中水溶性離子相關(guān)性分析

表3 水溶性離子與PM2.5 Pearson相關(guān)系數(shù)

** 在0.01水平(雙側(cè))上顯著相關(guān)； * 在0.05水平(雙側(cè))上顯著相關(guān).

(3)

(4)

圖和的相關(guān)性Fig.4 Correlations between and

較低時(shí)，有利于顆粒物中NH4NO3的形成.另外，也有研究表明，NOR與光照強(qiáng)度、大氣中氧化自由基、H2O2以及臭氧等有關(guān)[37].如表4所示，溫州市區(qū)四季NOR平均值均大于0.1，年均值為0.13±0.04，說明存在二次轉(zhuǎn)化.冬、春兩季NOR值相對(duì)較高，可能主要受到溫度的影響.

表4 PM2.5中SOR和NOR的水平

2.6 主成分分析

采用主成分分析法(principal component analysis, PCA)對(duì)溫州市PM2.5樣品中水溶性離子進(jìn)行源解析，從而對(duì)PM2.5中水溶性離子的來源做定性分析.主成分分析采用SPSS 19.0完成，分析結(jié)果見表5.

表5 因子載荷矩陣

溫州市包含4家主要的燃煤發(fā)電廠(浙能樂清電廠、浙能溫州電廠、溫州特魯萊電廠以及華潤電力)，主要工業(yè)為合成革、塑料、服裝、電器、化工、化纖、印染和造紙等，雖然工業(yè)燃燒用煤量遠(yuǎn)小于燃煤發(fā)電廠，但工業(yè)燃燒不夠完全，污染物去除效率遠(yuǎn)低于火力發(fā)電，因此，工業(yè)燃煤污染對(duì)環(huán)境空氣的貢獻(xiàn)也較大.根據(jù)溫州市國民經(jīng)濟(jì)和社會(huì)發(fā)展統(tǒng)計(jì)公報(bào)，2015年年末全市戶籍總?cè)丝?11.21萬，其中市區(qū)人口165.93萬；年末溫州市機(jī)動(dòng)車保有量202.68萬輛，較2014年年末增加14.45萬輛；全市房屋施工面積4.650 82×107m2；全市糧食播種面積為12.294×104hm2(184.41萬畝)；國民經(jīng)濟(jì)三次產(chǎn)業(yè)結(jié)構(gòu)的比重分別為2.7%(第一產(chǎn)業(yè))、45.5%(第二產(chǎn)業(yè))和51.8%(第三產(chǎn)業(yè)).根據(jù)主成分分析結(jié)果，結(jié)合溫州市實(shí)際情況，溫州市PM2.5中水溶性離子主要來源于燃煤(包括火力發(fā)電和工業(yè)燃燒過程)、機(jī)動(dòng)車尾氣、生物質(zhì)燃燒以及道路和建筑揚(yáng)塵，另外顆粒物中F-主要來源于紡織、造紙和涂料等行業(yè).

3 結(jié) 論

3.3 溫州市SOR和NOR的年均值分別為0.44±0.09和0.13±0.04，且夏秋季SOR大于春冬季，NOR小于春冬季.

3.4 根據(jù)主成分分析結(jié)果，結(jié)合實(shí)際情況，可知溫州市PM2.5中水溶性離子主要來源于燃煤(包括火力發(fā)電和工業(yè)燃燒過程)、機(jī)動(dòng)車尾氣、生物質(zhì)燃燒以及道路和建筑揚(yáng)塵，另外顆粒物中F-主要來源于紡織、造紙和涂料等行業(yè).

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GE Linlin1， ZHENG Yuanzhu2， TU Shengfeng2， ZHU Jingke3， WANG Qiaoli4， WANG Xiangqian3， LI Sujing3， LI Wei1,3

(1.InstituteofEnvironmentalEngineering,ZhejiangUniversity,Hangzhou310058,China; 2.WenzhouEnvironmentalMonitoringCenter,Wenzhou325003,China; 3.BiomassChemicalIndustryMinistryofEducationKeyLaboratory,InstituteofIndustrialEcologyandEnvironment,ZhejiangUniversity,Hangzhou310027,China; 4.InstituteofThermalPowerEngineering,ZhejiangUniversity,Hangzhou310027,China)

Wenzhou; PM2.5; water-soluble ions; pollution characteristics; source apportionment

2016-03-14.

葛琳琳(1991-)，ORCID:http//orcid.org/0000-0002-8908-4292，女，碩士研究生，主要從事PM2.5源解析研究， E-mail: gll920@zju.edu.cn.

*通信作者，ORCID:http://orcid.org/0000-0002-7757-3881，E-mail:sujing-li@zju.edu.cn.

10.3785/j.issn.1008-9497.2017.01.016

X 51

A

1008-9497(2017)01-112-09