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

化工教育部重點實驗室 工業(yè)生態(tài)與環(huán)境研究所，浙江 杭州 310027； 4.浙江大學 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)濟發(fā)展較快的城市之一.隨著城市化進程的加快以及工業(yè)的迅速發(fā)展，灰霾、酸雨和光化學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，其大氣首要超標污染物為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)設置4個采樣點，分4個季度采集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，對了解溫州市大氣復合污染特征、制定有效的防治對策具有重要意義.

1 材料與方法

1.1 樣品采集

為全面評價溫州主城區(qū)(鹿城區(qū)、甌海區(qū)和龍灣區(qū))大氣細顆粒物的污染現(xiàn)狀，根據(jù)《環(huán)境空氣顆粒物源解析監(jiān)測技術(shù)方法指南(試行)》(以下簡稱指南)的規(guī)定，在溫州市區(qū)范圍內(nèi)布設4個國控(或省控)監(jiān)測點位，溫州市環(huán)境監(jiān)測中心站(簡稱市站)、溫州市環(huán)境監(jiān)測中心站甌海分站(簡稱甌海)、龍灣區(qū)環(huán)境空氣監(jiān)測點(簡稱龍灣)以及南浦環(huán)境空氣監(jiān)測點(簡稱南浦)進行環(huán)境受體樣品采集.4個采樣點均位于溫州市主城區(qū).市站點位于鹿城區(qū)，南浦和甌海點位于甌海區(qū)，龍灣點位于龍灣區(qū)；市站采樣點位于甌江邊，周圍是學校和居民區(qū)，大氣污染來源相對較少；南浦采樣點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公司；龍灣點位于甌江附近的居民區(qū)，周邊有一些機械閥門鑄造企業(yè)和混凝土企業(yè).4個站點同步采集得到的環(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)測點分布見圖1.

根據(jù)指南中對采樣時間及周期的規(guī)定，本項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4個采樣點進行同步PM2.5采樣.使用嶗應2030型智能TSP中流量采樣器采樣，設置采樣流量為100 L·min-1.采集的樣品量應滿足分析要求且不過載，設置采樣時間為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，準確度≤±5.0%，流量相對標準偏差≤2.0%；

計前溫度：-30～99 ℃，分辨率0.1 ℃，準確度≤±1.0 ℃；

大氣壓：70～130 kPa，分辨率0.01 kPa，準確度≤±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)測點位分布示意Fig.1 Sampling sites of PM2.5 in Wenzhou City

執(zhí)行標準:HJ 618-2011《環(huán)境空氣PM10和PM2.5的測定重量法》,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，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，恒重條件設為溫度(20±1) ℃、相對濕度(50±5)%RH.平衡后用萬分之一分析天平稱重.

1.3 樣品預處理及分析

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)對濾液中的水溶性離子進行分析.

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)值低于檢測限.

2.2 PM2.5中水溶性離子時空變化特征

圖2 2015年觀測期間溫州市區(qū)PM2.5中水溶性離子的時空分布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，有利于顆粒物中NH4NO3的形成.另外，也有研究表明，NOR與光照強度、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)對溫州市PM2.5樣品中水溶性離子進行源解析，從而對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，污染物去除效率遠低于火力發(fā)電，因此，工業(yè)燃煤污染對環(huán)境空氣的貢獻也較大.根據(jù)溫州市國民經(jīng)濟和社會發(fā)展統(tǒng)計公報，2015年年末全市戶籍總?cè)丝?11.21萬，其中市區(qū)人口165.93萬；年末溫州市機動車保有量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)、機動車尾氣、生物質(zhì)燃燒以及道路和建筑揚塵，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)、機動車尾氣、生物質(zhì)燃燒以及道路和建筑揚塵，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