融冰過(guò)程中鐵離子和錳離子的遷移規(guī)律

張 巖,任方云,唐元慶,趙萬(wàn)里,趙同國(guó),劉同帥,劉玉燦,SHEN Hung Tao

融冰過(guò)程中鐵離子和錳離子的遷移規(guī)律

張 巖1*,任方云1,唐元慶1,趙萬(wàn)里1,趙同國(guó)1,劉同帥1,劉玉燦1,SHEN Hung Tao2

(1.煙臺(tái)大學(xué)土木工程學(xué)院,山東 煙臺(tái) 264005；2.克拉克森大學(xué)土木與環(huán)境工程系,美國(guó) 波茨坦 13699-5710)

為探究融冰過(guò)程中重金屬離子的遷移規(guī)律,選擇鐵離子和錳離子為研究對(duì)象,開(kāi)展了室內(nèi)模擬融冰實(shí)驗(yàn),探討其在融冰過(guò)程中的遷移規(guī)律,并分析初始濃度和冷凍溫度對(duì)其遷移過(guò)程的影響.結(jié)果表明:在不同的初始濃度和冷凍溫度條件下,鐵離子和錳離子在冰中各層的濃度分布關(guān)系皆為:中層<上層<下層;融冰過(guò)程中,51.17%～71.67%的鐵離子和錳離子均在冰體融化前期(0～25%)集中釋放,中后期相對(duì)平穩(wěn)均勻釋放,此外初始濃度對(duì)冰融化時(shí)鐵離子和錳離子的遷移規(guī)律影響不大,而冷凍溫度較低時(shí),融1中鐵離子和錳離子的濃度基本在增加;融冰過(guò)程中,隨著累積融水體積的增加,融水中鐵離子和錳離子的濃度與冰體初始濃度之比逐漸降低,它們之間呈指數(shù)函數(shù)衰減模式.

融冰；鐵離子；錳離子；遷移規(guī)律

中國(guó)北方冬季漫長(zhǎng)而寒冷,湖泊、水庫(kù)和河流等每年有3～5個(gè)月的時(shí)間被冰雪覆蓋[1-2].水體結(jié)冰過(guò)程中,水中的污染物會(huì)被截留在冰體中[3-4].翌年初春冰逐漸融化,導(dǎo)致冰中的污染物被釋放出來(lái),成為承納水體的污染源,甚至?xí)谒w沉積物中積累[5-6],對(duì)水環(huán)境產(chǎn)生威脅.隨著全球氣候逐漸變暖[7],寒冷地區(qū)水體的冰封期縮短,冰川融化加速,這使得研究融化過(guò)程中污染物的遷移規(guī)律迫在眉睫.

現(xiàn)已公開(kāi)的有關(guān)淡水研究的文獻(xiàn)中,只有2%涉及水體結(jié)冰過(guò)程[8],且主要集中在氮、磷、金屬離子,有機(jī)污染物等物質(zhì)研究[9-13].關(guān)于融冰過(guò)程研究的文獻(xiàn)相對(duì)匱乏,近些年僅有的一些文獻(xiàn)多集中于有機(jī)污染物釋放[14-17]和融水對(duì)微生物的影響[18-20].如Xue等[21]評(píng)估了融化冰中溶解有機(jī)物(DOM)的洗脫行為,結(jié)果表明DOM融化過(guò)程中表現(xiàn)出早期洗脫現(xiàn)象;李志軍等[22]研究發(fā)現(xiàn)融化過(guò)程中,冰內(nèi)硝基苯“原位不動(dòng)”,冰內(nèi)的硝基苯不發(fā)生遷移,只隨冰的融化遷移到水體中.Kanna等[23]將含有一定量鐵的海水與海冰一起冷凍,以評(píng)估海冰融化釋放出的鐵中哪些有利于浮游植物的生長(zhǎng).而關(guān)于融冰過(guò)程中重金屬離子釋放的研究還鮮有報(bào)道.鐵離子和錳離子作為最常見(jiàn)的2種過(guò)渡重金屬,它們以各種溶解態(tài)離子的形式存在于水生環(huán)境中,過(guò)量的鐵離子和錳離子不僅會(huì)引起視覺(jué)問(wèn)題,也會(huì)通過(guò)食物鏈的放大影響生物體的健康[24].基于此,本研究以鐵離子和錳離子為對(duì)象,開(kāi)展了室內(nèi)模擬融冰實(shí)驗(yàn),探討其在融冰過(guò)程中的遷移規(guī)律,并分析初始濃度和冷凍溫度對(duì)其遷移過(guò)程的影響,以期明確融冰過(guò)程對(duì)水體環(huán)境的影響,引起人們對(duì)融冰過(guò)程環(huán)境效應(yīng)的關(guān)注.

1 材料與方法

1.1 實(shí)驗(yàn)裝置

為模擬自然水體自上而下的結(jié)冰過(guò)程,本研究采用一種自制的敞口單向?qū)Ю浣Y(jié)冰模擬裝置(圖1).將水樣裝入圓柱形玻璃桶(10cm、29.5cm),玻璃桶四周及底部用聚苯乙烯泡沫(EPS)保溫材料包裹以阻斷桶體與外界進(jìn)行熱量傳遞,確保冰體自上而下逐漸生長(zhǎng),將上述裝置置于帶溫度控制的低溫實(shí)驗(yàn)箱中.將獲得的冰樣放入帶有圓柱形玻璃壁的融冰裝置中融化,收集冰融水.

圖1 結(jié)冰裝置(左)與融冰裝置(右)

1-玻璃桶;2-EPS保溫材料;3-低溫實(shí)驗(yàn)箱;4-冰樣;5-帶玻璃圓筒的漏斗;6-融冰水樣

1.2 藥品與檢測(cè)

主要藥品:硫酸亞鐵銨、電解錳、乙酸鈉、鄰菲啰啉等,以上藥品均為分析純,生產(chǎn)廠家為煙臺(tái)北聯(lián).

檢測(cè)方法:所有樣品3個(gè)平行,樣品中鐵離子和錳離子總量的檢測(cè)方法均按照《水和廢水檢測(cè)方法》(第四版)[25]進(jìn)行檢測(cè),檢測(cè)結(jié)果的標(biāo)準(zhǔn)差控制在5%以內(nèi).

1.3 實(shí)驗(yàn)設(shè)計(jì)

為了探究融冰過(guò)程中金屬離子的遷移規(guī)律,選取鐵離子和錳離子為研究對(duì)象,探究不同初始濃度(A組)和不同結(jié)冰溫度(B組)對(duì)其釋放規(guī)律的影響.

將A組分為A1組(鐵離子)和A2組(錳離子).根據(jù)我國(guó)《生活飲用水衛(wèi)生標(biāo)準(zhǔn)》(GB5749-2006)[26]對(duì)鐵離子和錳離子的限制濃度,設(shè)定A1組的初始濃度為0.3, 0.6, 0.9, 1.2, 1.5mg/L,A2組的初始濃度為0.15, 0.3, 0.6, 1.2, 2.4mg/L,每種濃度的溶液各8L分別置于結(jié)冰模擬器中(占反應(yīng)器體積的4/5),置于-15℃的低溫箱中,當(dāng)冰厚達(dá)到12cm時(shí)取出,將所得的整個(gè)冰體置于25℃恒溫箱中連續(xù)融化,將冰融水根據(jù)融出的先后順序平均分為4份,依次定義為融1,融2,融3,融4,檢測(cè)融水樣品中鐵離子和錳離子的濃度.由于金屬離子在冰體中的分布情況也會(huì)影響其在融冰過(guò)程中的遷移,為此,以上述同樣的方式獲得冰樣,將所得冰樣樣本每4cm進(jìn)行分層,定義0～4cm為上層,4～8cm為中層,8～12cm為下層,分別置于燒杯中在25℃恒溫箱中條件下融化,然后檢測(cè)鐵離子和錳離子的濃度.

將B組分為B1組(鐵離子)和B2組(錳離子).B1組的初始濃度為0.6mg/L,B2組的初始濃度為0.3mg/L,各配置40L,每種溶液各取8L分別置于結(jié)冰模擬器中(占反應(yīng)體積的4/5),分別置于-5, -10, -15, -20和-25℃的低溫箱中,當(dāng)冰厚達(dá)到12cm時(shí)取出,將所得的整個(gè)冰體置于25℃恒溫箱中連續(xù)融化,根據(jù)冰融水融出的先后順序平均分為4份,依次定義為融1,融2,融3,融4,檢測(cè)融水樣品中鐵離子和錳離子的濃度.由于金屬離子在冰體中的分布情況也會(huì)影響其在融冰過(guò)程中的遷移,為此,以上述同樣的方式獲得冰樣,將所得冰樣樣本每4cm進(jìn)行分層,定義0～4cm為上層,4～8cm為中層,8～12cm為下層,分別置于燒杯中在25℃恒溫箱中條件下融化,然后檢測(cè)鐵離子和錳離子的濃度.

1.4 分析方法

采用濃度系數(shù)()描述冰融化過(guò)程中鐵離子和錳離子的濃度規(guī)律,該濃度系數(shù)定義為每等份融水中離子濃度與冰體中離子的總濃度之比,即

式中:C為每等份融水中離子濃度, mg/L,=1、2、3、4,依次為融1,融2,融3,融4,ice為冰相中離子的總濃度, mg/L.

采用融出率()從質(zhì)量的角度描述冰融化過(guò)程中鐵離子和錳離子的遷移能力,該融出率定義為每等份融水中離子的質(zhì)量與冰體中離子的總質(zhì)量之比,即:

式中:m為每等份融水中離子質(zhì)量, mg,=1、2、3、4,依次為融1,融2,融3,融4,ice為冰相中離子的總質(zhì)量, mg.

2 結(jié)果與討論

2.1 鐵離子和錳離子在冰體中的分布

當(dāng)水體結(jié)冰時(shí),冰生長(zhǎng)速率較快,鐵離子和錳離子會(huì)來(lái)不及遷移到冰下水體而被截留在冰體里[27-28].被截留的鐵離子和錳離子在冰中的分布會(huì)決定它們?cè)诔跞跁r(shí)期能否形成連通的排水通道,并且在初融時(shí)期,分布在冰體不同部位的鐵離子和錳離子是隨機(jī)選擇某些排水通道融出[29].因此,冰晶內(nèi)和冰晶上鐵離子和錳離子的分布對(duì)融水成分至關(guān)重要[30],在探究融冰過(guò)程中鐵離子和錳離子的遷移規(guī)律前,需要對(duì)冰體里鐵離子和錳離子的分布情況進(jìn)行研究.

如圖2所示,鐵離子和錳離子在冰中分布濃度關(guān)系為:中層<上層<下層,即鐵離子和錳離子在冰中的分布隨冰厚的增加呈現(xiàn)C型分布[31-32].這是由于結(jié)冰初期冰體生長(zhǎng)速率較快,容易形成樹(shù)枝狀冰,這種結(jié)構(gòu)冰易捕獲鐵離子和錳離子,因此冰上層鐵離子和錳離子濃度較高[33].隨著結(jié)冰的進(jìn)行,冰厚的增加減弱了與外界的熱量交換,冰生長(zhǎng)速率較低,樹(shù)枝狀冰不易形成或者量較少,使得中層冰體里的鐵離子和錳離子含量較少.由于冷凍濃縮的影響,越靠近冰水界面的冰體自然捕獲的鐵離子和錳離子要多,所以底層離子含量要大于上層和中層[34].此外,鐵離子和錳離子在冰體中的濃度與初始濃度呈正相關(guān),與冷凍溫度呈負(fù)相關(guān),即隨著初始濃度的增大,冷凍溫度的降低,鐵離子和錳離子在冰體中的濃度也逐漸增加.這是因?yàn)槔鋬鰷囟仍降?冰的生長(zhǎng)速率越高,而初始濃度越高,也使得溶液中潛在晶核數(shù)量增多,晶核互相碰撞的頻率和能量增加,二次成核概率增加,冰晶生長(zhǎng)速度加快,導(dǎo)致冰純度降低[35].

圖2 不同初始濃度和不同冷凍溫度下鐵、錳離子在冰體中的分布

A:初始濃度;B:冷凍溫度;1:鐵離子;2:錳離子

2.2 鐵離子和錳離子在融冰過(guò)程中的遷移規(guī)律

由圖3～4可知,在冰的融化過(guò)程中,鐵離子和錳離子的濃度隨著融化比率的增加逐漸降低,即融1>融2>融3>融4.冰體中的鐵離子和錳離子在初期(0～25%)會(huì)釋放51.17%～71.67%,初期融水的濃度系數(shù)在1.85～2.89之間.

冰融化時(shí)鐵離子和錳離子集中釋放可以從3個(gè)角度解釋:(1)從鐵離子和錳離子在冰中的分布來(lái)看,結(jié)冰過(guò)程中,被捕獲在冰體里的鐵離子和錳離子是存在于晶體的表面或者冰晶界處,當(dāng)表層冰開(kāi)始融化時(shí),初期會(huì)融出大量鐵離子和錳離子,后期融出來(lái)的是來(lái)自被困在晶體內(nèi)部的鐵離子和錳離子,其含量較少[36-37],所以不同初始濃度和不同冷凍溫度下所獲得的冰體在融化過(guò)程中,鐵離子和錳離子均呈現(xiàn)前期集中釋放,中后期相對(duì)平穩(wěn)均勻釋放.(2)從冰融化機(jī)理來(lái)看,鐵離子和錳離子被捕獲在冰晶里時(shí)會(huì)以液袋的形式存在,隨著溫度的逐漸升高,冰體開(kāi)始瓦解,液袋慢慢向下移動(dòng),冰內(nèi)部之間會(huì)形成類似樹(shù)干和樹(shù)枝的流動(dòng)線, 稱為排水通道,鐵離子和錳離子慢慢就沿著排水通道融出[38].為了示蹤排水通道,在-15℃將1.6L的1mg/L的紫紅色高錳酸鉀溶液完全凍結(jié),然后切片在普通光學(xué)顯微鏡下40倍觀察,如圖5所示,被截留在冰體里的高錳酸鉀以液袋的形式存在,在初融之際,許多液袋會(huì)慢慢貫穿成一條一條排水通道.(3)從熱力學(xué)的角度來(lái)看,為了維持溫度和濃度之間的熱力學(xué)平衡,排水通道的熱量傳遞由與液相體積增加相關(guān)的潛熱變化控制,所以,鐵離子和錳離子通過(guò)排水通道的傳質(zhì)速率對(duì)傳熱速率只有二級(jí)影響,對(duì)“被困在排水通道周圍冰體中的溶液”的洗滌速率也只有二級(jí)影響[39].接著在較小的流速下,分子擴(kuò)散會(huì)導(dǎo)致雜質(zhì)的擴(kuò)散,從而導(dǎo)致高濃度的鐵離子和錳離子和少量融化液排出[40].

圖3 不同濃度和不同冷凍溫度下鐵、錳離子的濃度系數(shù)

A:初始濃度;B:冷凍溫度;1:鐵離子;2:錳離子

此外,由圖3～4可知,初始濃度對(duì)冰融化時(shí)鐵離子和錳離子的遷移規(guī)律影響不大,而冷凍溫度較低時(shí),融1中鐵離子和錳離子的濃度基本在增加.這是由于在緩慢的凍結(jié)速度下,冰晶是以柱狀形式生長(zhǎng),冰水界面是平面的.在更快的冷凍速度下,冰晶以樹(shù)枝狀結(jié)構(gòu)生長(zhǎng)[41],此類樹(shù)枝狀結(jié)構(gòu)會(huì)捕獲更多的離子.最后冰體在融化初期,自然會(huì)有更多的離子袋逐漸向下移動(dòng),在冰體內(nèi)形成了更多的上下貫通的排水通道.如圖5所示, 當(dāng)排水通道貫穿整個(gè)冰體時(shí),鐵離子和錳離子沿著重力的方向流失,頂部的通道會(huì)消失,導(dǎo)致在融化結(jié)束時(shí)剩余的冰體更純,融水的濃度更高.當(dāng)排水通道沒(méi)有整個(gè)貫穿冰體時(shí),只有冰體逐漸融化直至排水通道暴露在冰體底部,鐵離子和錳離子才會(huì)隨融水流出[42].

圖4 不同濃度和不同冷凍溫度下鐵、錳離子的融出率

A:初始濃度;B:冷凍溫度;1:鐵離子;2:錳離子

圖5 排水通道示蹤顯微圖

×40 紅色:高錳酸鉀;黑色圓圈:氣泡

2.3 融冰過(guò)程中鐵離子和錳離子的濃度模型

為了定量描述融冰中鐵離子和錳離子的遷移規(guī)律,將不同溫度和不同濃度下的融水?dāng)?shù)據(jù)處理后使用origin2018進(jìn)行擬合結(jié)果發(fā)現(xiàn), 隨著融水累積體積比的增加,融水中鐵離子和錳離子濃度與冰體濃度之比降低,它們之間的關(guān)系呈指數(shù)衰減[43],如圖6所示,擬合參數(shù)見(jiàn)表1～4,判定系數(shù)2值在0.994～ 0.999之間,其一般通式為:

式中: x為累積融水體積比; y為融水中鐵離子和錳離子濃度與冰體濃度之比; A、t和y0在某一冷凍溫度或某一初始濃度下為常數(shù),由表1～4可知,它們受初始濃度,冷凍溫度,離子的種類的影響.此外,從圖6可以看出,不同濃度或不同溫度下的擬合曲線都比較密集,因此,溫度或濃度對(duì)其遷移趨勢(shì)影響不大.可以根據(jù)此指數(shù)衰減模型預(yù)估在一定溫度或初始濃度值下融冰過(guò)程中某一融水體積比的濃度.此指數(shù)衰減模型也清晰地反映出冰融化時(shí),污染物釋放的速度,這可為融水對(duì)自然水體影響的研究提供參考,進(jìn)而也可為冰川融化形成的徑流對(duì)湖泊或河流造成的危害帶來(lái)思考.

A:初始濃度;B:冷凍溫度;1:鐵離子;2:錳離子

表1 不同濃度的鐵離子擬合參數(shù)

表2 不同濃度的錳離子擬合參數(shù)

表3 不同溫度的鐵離子擬合參數(shù)

表4 不同溫度的錳離子擬合參數(shù)

3 結(jié)論

3.1 在不同的初始濃度和冷凍溫度條件下,鐵離子和錳離子在冰中各層的濃度分布關(guān)系為:中層<上層<下層,呈C型分布.

3.2 51.17%～71.67%的鐵離子和錳離子均在冰體融化前期(0～25%)集中釋放,中后期相對(duì)平穩(wěn)均勻釋放;初始濃度對(duì)冰融化時(shí)鐵離子和錳離子的遷移規(guī)律影響不大,而冷凍溫度較低時(shí),融1中鐵離子和錳離子的濃度基本在增加.

3.3 在融化過(guò)程中,鐵離子和錳離子的濃度與冰體初始濃度之比隨著累積融水體積的增加呈指數(shù)函數(shù)衰減模式.

3.4 在融化過(guò)程中,影響鐵離子和錳離子的釋放的因素除了初始濃度和冷凍溫度外可能還有其它因素,如融冰溫度,凍融循環(huán)次數(shù)和離子半徑等,這還有待進(jìn)一步探討.

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Migration of iron and manganese ions during ice melting.

ZHANG Yan1*, REN Fang-yun1, TANG Yuan-qing1, ZHAO Wan-li1, ZHAO Tong-guo1, LIU Tong-shuai1, LIU Yu-can1, SHEN Hung-tao2

(1.School of Civil Engineering, Yantai University, Yantai 264005, China；2.Department of Civil and Environmental Engineering, Clarkson University, Potsdam New York 13699-5710, USA)., 2021,41(5)：2391～2398

In order to explore the migration law of heavy metal ions in the process of ice melting, indoor simulated ice melting experiments were carried out to study the migration law with iron and manganese ions as example metal ions, and the effects of initial concentration and freezing temperature on the migration process were also analyzed. The results showed that under different initial concentrations and freezing temperatures, the concentration distribution of iron and manganese ions in ice was as follows: middle layer < upper layer < lower layer; In the process of ice melting, 51.17%～71.67% of iron and manganese ions were released in the early stage of ice melting (0～25%), and in the middle and late stages, iron and manganese ions were released stably and evenly. In addition, the initial concentration had little effect on the migration of iron and manganese ions during ice melting. When the freezing temperature was low, the concentration of iron and manganese ions increased basically in melt 1. In the process of ice melting, with the increase of accumulated melt water volume, the ratio of the concentration of iron ion and manganese ion in melt water to initial concentration of ice body gradually decreased, and showed an exponential function attenuation mode.

ice melting；iron ion；manganese ion；migration law

X524

A

1000-6923(2021)05-2391-08

張 巖(1984-),男,山東平度人,副教授,博士,主要研究方向?yàn)樗Y源利用與保護(hù).發(fā)表論文30余篇.

2020-09-28

國(guó)家自然科學(xué)基金資助項(xiàng)目(51609207);山東省重點(diǎn)研發(fā)計(jì)劃 (2019GHY112033);山東省優(yōu)秀中青年科學(xué)家科研獎(jiǎng)勵(lì)基金資助項(xiàng)目(BS2014HZ021;ZR2017BEE016)

* 責(zé)任作者, 副教授, zhangyan-992@163.com