我國(guó)六價(jià)鉻淡水水生生物安全基準(zhǔn)推導(dǎo)研究

廖靜，梁峰，楊紹貴，何歡，孫成,*，高世祥，崔益斌

1. 南京大學(xué)環(huán)境學(xué)院，南京 210023 2. 河南城建學(xué)院，平頂山 467036

我國(guó)六價(jià)鉻淡水水生生物安全基準(zhǔn)推導(dǎo)研究

廖靜1，梁峰2，楊紹貴1，何歡1，孫成1,*，高世祥1，崔益斌1

1. 南京大學(xué)環(huán)境學(xué)院，南京 210023 2. 河南城建學(xué)院，平頂山 467036

參照美國(guó)國(guó)家環(huán)境保護(hù)局(USEPA)“推導(dǎo)保護(hù)水生生物及其用途的國(guó)家水質(zhì)基準(zhǔn)的技術(shù)指南”的程序和規(guī)范，篩選了我國(guó)廣泛存在的淡水水生生物物種，收集現(xiàn)有的急性和慢性毒性數(shù)據(jù)，結(jié)合課題組實(shí)驗(yàn)得到的部分本土生物毒性數(shù)據(jù)，分別采用物種敏感度排序法(SSR)、物種敏感度分布法(SSD)以及澳大利亞的水質(zhì)基準(zhǔn)技術(shù)方法對(duì)我國(guó)六價(jià)鉻的淡水水生生物安全基準(zhǔn)進(jìn)行了推導(dǎo)。獲得了我國(guó)淡水水生生物的六價(jià)鉻的雙值基準(zhǔn)，3種方法得到的基準(zhǔn)最大濃度(CMC)分別為23.97、22.84、29.06 μg·L-1，基準(zhǔn)連續(xù)濃度(CCC)分別為14.63、10.35、9.00 μg·L-1，在同一個(gè)數(shù)量級(jí)上，但與美國(guó)的基準(zhǔn)值有一些差異，建議使用SSD法推導(dǎo)CMC值和CCC值。研究結(jié)果可為我國(guó)水質(zhì)基準(zhǔn)的制定提供一些有用的基礎(chǔ)資料。

六價(jià)鉻；淡水水生生物；水質(zhì)基準(zhǔn)；基準(zhǔn)最大濃度(CMC)；基準(zhǔn)連續(xù)濃度(CCC)

水質(zhì)基準(zhǔn)是制定水質(zhì)標(biāo)準(zhǔn)的科學(xué)依據(jù)，在水環(huán)境保護(hù)方面發(fā)揮著非常重要的作用。頒布水質(zhì)基準(zhǔn)的目的在于防止污染物對(duì)重要的商業(yè)和娛樂水生生物，以及其他重要物種如河流湖泊中的魚、底棲無脊椎動(dòng)物和浮游生物造成不可接受的長(zhǎng)期和短期的效應(yīng)[1]。水生生物安全基準(zhǔn)的制定需要根據(jù)各區(qū)域水環(huán)境生物區(qū)系特點(diǎn)，選擇適當(dāng)?shù)拇硇晕锓N用于水生生物安全基準(zhǔn)的推導(dǎo)，以使得基于區(qū)域水環(huán)境代表性水生生物而得出的基準(zhǔn)推導(dǎo)值可以為大多數(shù)生物提供適當(dāng)保護(hù)。中國(guó)無論從水質(zhì)上還是從水生態(tài)系統(tǒng)的結(jié)構(gòu)特征上與國(guó)外都有著明顯的差異，僅依靠國(guó)外的基準(zhǔn)或是標(biāo)準(zhǔn)來制定我國(guó)的水質(zhì)標(biāo)準(zhǔn)，很難為不同水域的生物提供全面的、有效的保護(hù)。因此從維護(hù)水生態(tài)系統(tǒng)的長(zhǎng)遠(yuǎn)利益與保護(hù)水環(huán)境的可靠性來看，開展中國(guó)的水質(zhì)基準(zhǔn)研究，制定我們國(guó)家自己的國(guó)家水質(zhì)基準(zhǔn)勢(shì)在必行。正是基于上述因素，我國(guó)從“十一五”開始，逐步開展了基于我國(guó)的水生生物研究，金小偉等[2]探討了適用于我國(guó)的水質(zhì)基準(zhǔn)計(jì)算方法及推導(dǎo)流程，并討論了推導(dǎo)過程中可能存在的問題；雷炳莉等[3]運(yùn)用3種方法對(duì)太湖流域中五氯酚、2,4-二氯酚及2,4,6-三氯酚進(jìn)行水質(zhì)基準(zhǔn)推導(dǎo)，并且比較3種方法推導(dǎo)值的差異，提出建立我國(guó)的水質(zhì)基準(zhǔn)不能僅依靠國(guó)外的水質(zhì)基準(zhǔn)或標(biāo)準(zhǔn)；雷炳莉等[4]采用評(píng)估因子法和物種敏感度分布曲線法對(duì)3種不同的4-壬基酚進(jìn)行水質(zhì)基準(zhǔn)推導(dǎo)和比較，提出收集毒性數(shù)據(jù)應(yīng)有針對(duì)性，明確選擇毒性數(shù)據(jù)的測(cè)量終點(diǎn)；中國(guó)環(huán)境科學(xué)研究院的吳豐昌、閆振廣等[5-9]已經(jīng)開展了大量的水質(zhì)基準(zhǔn)研究，吳豐昌等[7]對(duì)鋅的毒性數(shù)據(jù)進(jìn)行分類來研究基準(zhǔn)，發(fā)現(xiàn)不同類別的物種對(duì)鋅的敏感性存在顯著性差異，其中甲殼類動(dòng)物最為敏感。目前，我國(guó)的水質(zhì)基準(zhǔn)研究已積累了一定的理論基礎(chǔ)與實(shí)踐經(jīng)驗(yàn)。

鉻是14種最有害的重金屬之一。由于鉻的毒性較高，鉻及其化合物被列入中國(guó)水環(huán)境優(yōu)先污染物黑名單。鉻在環(huán)境中穩(wěn)定存在的2種價(jià)態(tài)Cr(Ⅲ)和Cr(Ⅵ)卻有著不同的性質(zhì)，適量的Cr(Ⅲ)可以降低人體血漿中的血糖濃度，提高人體胰島素活性，促進(jìn)糖和脂肪代謝，提高人體的應(yīng)激反應(yīng)能力等。而Cr(Ⅵ)則是一種強(qiáng)氧化劑，具有強(qiáng)致癌變、致畸變、致突變作用，對(duì)生物體傷害較大[10]。通常認(rèn)為六價(jià)鉻的毒性比三價(jià)鉻的毒性高100倍。正是由于具有較大的生物毒性，因此，對(duì)于六價(jià)鉻毒性作用的研究一直得到人們的重視。基于此，本文運(yùn)用物種敏感度排序法(SSR)、以及荷蘭和澳大利亞的水質(zhì)基準(zhǔn)的技術(shù)方法對(duì)中國(guó)水生生物物種(包括中國(guó)本地種及引進(jìn)物種等)的六價(jià)鉻毒性數(shù)據(jù)進(jìn)行了研究，以期獲得更為適合我國(guó)的淡水水生生物六價(jià)鉻基準(zhǔn)，并為中國(guó)六價(jià)鉻水質(zhì)標(biāo)準(zhǔn)的制定提供參考。

1 材料與方法(Materials and methods)

1.1 物種與數(shù)據(jù)的篩選

本文基本采用美國(guó)國(guó)家環(huán)境保護(hù)局(USEPA)規(guī)定的物種選擇原則，同時(shí)考慮到中國(guó)的魚類以鯉科為主，特別注意收集了鯉科魚類的六價(jià)鉻毒性數(shù)據(jù)，同時(shí)收集在我國(guó)已廣泛繁殖和存在的引進(jìn)物種的六價(jià)鉻毒性數(shù)據(jù)。六價(jià)鉻的毒性數(shù)據(jù)主要來源于美國(guó)鉻的水質(zhì)基準(zhǔn)技術(shù)文件[11]、USEPA的ECOTOX毒性數(shù)據(jù)庫(kù)(http://cfpub.epa.gov/ecotox/)和中國(guó)知網(wǎng)(http://www.cnki.net)以及維普數(shù)據(jù)庫(kù)數(shù)據(jù)(http://www.cqvip.com/)，數(shù)據(jù)收集截止到2013年11月。

對(duì)于部分難于獲得數(shù)據(jù)的本土生物，本課題組開展相應(yīng)急慢性毒性試驗(yàn)，實(shí)驗(yàn)室試驗(yàn)物種主要有鰱魚、鯽魚、黃顙魚、林蛙蝌蚪、中華園田螺、青蝦等本土生物。

數(shù)據(jù)收集后，根據(jù)USEPA基準(zhǔn)技術(shù)指南和相關(guān)準(zhǔn)則[1,11]，將不符合水質(zhì)基準(zhǔn)計(jì)算要求的試驗(yàn)數(shù)據(jù)剔除，其中包括非中國(guó)物種的試驗(yàn)數(shù)據(jù)，用去離子水作為試驗(yàn)用水的試驗(yàn)數(shù)據(jù)和實(shí)驗(yàn)設(shè)計(jì)不科學(xué)或者不符合要求的試驗(yàn)數(shù)據(jù)。

1.2 水生生物試驗(yàn)方法

鰱魚、鯽魚、黃顙魚、林蛙蝌蚪、中華園田螺、青蝦的急性毒性測(cè)試試驗(yàn)主要參照了“GB/T 13267-1991 水質(zhì)物質(zhì)對(duì)淡水魚(斑馬魚)急性毒性測(cè)試方法”[12]以及“OECD化學(xué)品毒性測(cè)試技術(shù)指南”[13]，受試化合物選擇重鉻酸鉀，化學(xué)性質(zhì)穩(wěn)定，采用靜態(tài)試驗(yàn)，得出急性毒性的LC50值。

1.3 水質(zhì)基準(zhǔn)推導(dǎo)方法

1.3.1 物種敏感度排序法

USEPA的物種敏感度分布法(species sensitivity distribution, SSD)即雙值基準(zhǔn)法,是1978年USEPA的研究人員認(rèn)識(shí)到物種對(duì)污染物的敏感度是連續(xù)分布的，而且遵循類似于正態(tài)分布的概率模型[14]，因而提出用基于物種敏感度分布的方法代替專家判斷法來制定基準(zhǔn)，并且設(shè)定了95%的生物保護(hù)水平，后經(jīng)多次修訂，方法定形于1985年頒布的水生生物基準(zhǔn)技術(shù)指南中。該方法來源雖然是SSD曲線法，但在實(shí)際操作中，將復(fù)雜的SSD作圖的過程簡(jiǎn)化為公式計(jì)算，該法在有的文獻(xiàn)中也被稱為物種敏感度排序法(species sensitivity rank, SSR)[15]。

1.3.2 物種敏感度分布法

歐洲的SSD理論起源于Kooijman[16]對(duì)急性毒性值外推中安全因子的研究，提出了基于物種敏感度分布的基準(zhǔn)推算方法，但因理論不完善，得出的基準(zhǔn)值太低而無法在管理中使用。1989年，Van Straalen和Denneman[17]對(duì)其進(jìn)行了修正，通過設(shè)定HCp(hazardous concentration for p of the species)，即用(1-p)%物種的保護(hù)水平，去掉了函數(shù)曲線的“尾巴”，避免了基準(zhǔn)值過低的問題，歐美各國(guó)一般都默認(rèn)p值為5，那么HC5是指影響不超過5%的物種，即可以保護(hù)95%以上種群時(shí)對(duì)應(yīng)的濃度。至此，SSD理論基本成熟，之后Wagner和Lokke[18]以及Aldenberg和Slob[19]對(duì)該方法又作了進(jìn)一步修正，目前歐洲SSD技術(shù)的數(shù)學(xué)模型基礎(chǔ)為對(duì)數(shù)-正態(tài)分布或?qū)?shù)-邏輯斯蒂函數(shù)分布，澳大利亞/新西蘭也對(duì)SSD法進(jìn)行了修正，其運(yùn)用的主要數(shù)學(xué)模型基礎(chǔ)是Burr Type Ⅲ分布[20]。

2 結(jié)果與分析(Results and analysis)

2.1 毒性數(shù)據(jù)

毒性數(shù)據(jù)篩選后共得到36個(gè)屬46個(gè)物種的急性毒性數(shù)據(jù)(表1)、13個(gè)屬16個(gè)物種的慢性毒性數(shù)據(jù)(表2)、4個(gè)物種的淡水藻類和植物的毒性值(表3)以及生物體的生物富集因子(bio-concentration factor, BCF)(表4)，毒性數(shù)據(jù)符合建立基準(zhǔn)要求，選擇的水生生物測(cè)試種涵蓋3個(gè)營(yíng)養(yǎng)級(jí)：綠藻/初級(jí)生產(chǎn)者，小型甲殼類/初級(jí)消費(fèi)者，以及魚類/次級(jí)消費(fèi)者。選擇的水生生物測(cè)試種涵蓋至少3門8科的生物分類單元。

表1 六價(jià)鉻對(duì)淡水動(dòng)物的急性毒性Table 1 Acute toxicity of hexavalent chromium to aquatic organisms

注：SMAV即種急性毒性平均值；GMAV即屬急性毒性平均值。

Note: SMAV is species mean acute value; GMAV is genus mean acute value.

表2 六價(jià)鉻對(duì)淡水動(dòng)物的慢性毒性Table 2 Chronic toxicity of hexavalent chromium to aquatic organisms

注：SMCV即種慢性毒性平均值；GMCV即屬慢性毒性平均值。

Note: SMCV is species mean chronic value; GMCV is genus mean chronic value.

表3 六價(jià)鉻對(duì)淡水藻類和植物的毒性Table 3 Toxicity of hexavalent chromium to freshwater algae and plants

注：六價(jià)鉻的受試化合物選用重鉻酸鉀。

Note: the tested hexavalent chromium is potassium dichromate

表4 六價(jià)鉻在淡水生物體內(nèi)的富集系數(shù)(BCF)Table 4 Bioconcentration factors (BCF) of hexavalent chromium for aquatic organisms

2.2 水質(zhì)基準(zhǔn)推導(dǎo)

2.2.1 SSR法

SSR法是由USEPA推薦的制定水質(zhì)基準(zhǔn)的標(biāo)準(zhǔn)方法[1]，該法是把所獲得屬的毒性數(shù)據(jù)按從小到大的順序進(jìn)行排列，序列的百分?jǐn)?shù)P按公式P=R/(N+1)進(jìn)行計(jì)算，其中R是毒性數(shù)據(jù)在序列中的位置，N是所獲得的毒性數(shù)據(jù)量。選擇靠近排序百分?jǐn)?shù)為5%處的4個(gè)屬就是4個(gè)最敏感屬，然后根據(jù)公式(1)～(4)可得出排序百分?jǐn)?shù)為5%處所對(duì)應(yīng)的濃度，該濃度即為最終急性值(final acute value, FAV)，基準(zhǔn)最大濃度(criteria maximum concentration, CMC)=FAV/2。由于慢性數(shù)據(jù)量充足，最終慢性值(final chronic value, FCV)使用FAV相同的方法計(jì)算，基準(zhǔn)連續(xù)濃度(criteria continuous concentration, CCC)=min(FCV, FPV, FRV)，F(xiàn)PV (final plant value)即最終植物值，F(xiàn)RV (final residue value)即最終殘留值。

(1)

(2)

(3)

FAV=eA

(4)

式中GMAV為屬急性毒性平均值；P為選擇4個(gè)屬毒性數(shù)據(jù)的排序百分?jǐn)?shù)；S、L、A為計(jì)算中的符號(hào)，沒有特殊的含義。

根據(jù)表1的GMAV值，得出六價(jià)鉻的FAV是47.94 μg·L-1，即CMC的值為23.97 μg·L-1。根據(jù)表2的GMCV值，得出六價(jià)鉻的FCV是14.63 μg·L-1。從表3中可以看出，六價(jià)鉻對(duì)水生植物毒性范圍在84.3～13 000 μg·L-1之間，最敏感的毒性效應(yīng)值為84.3 μg·L-1，由此確定FPV為84.3 μg·L-1。從表4獲得的BCF值看，六價(jià)鉻在虹鱒魚肌肉和魚體內(nèi)的富集系數(shù)分別為小于1和1，表明鉻在魚體內(nèi)的富集作用不明顯，因此此處不再計(jì)算最終殘留值FRV。所以CCC的值是14.63 μg·L-1。

2.2.2 SSD法

用SSD法推導(dǎo)CMC和CCC時(shí)，首先對(duì)滿足條件的種平均急性值(表1)和種平均慢性值(表2)取對(duì)數(shù)后分別進(jìn)行正態(tài)分布檢驗(yàn)，運(yùn)用SPSS 19.0進(jìn)行正態(tài)分布檢驗(yàn)，結(jié)果表明，種平均急性值的對(duì)數(shù)值及種平均慢性值的對(duì)數(shù)值均符合正態(tài)分布。然后，用SSD法推導(dǎo)CMC時(shí)，對(duì)種平均急性值由小到大進(jìn)行排序并編號(hào)，以種平均急性值的對(duì)數(shù)值為橫坐標(biāo)，以每個(gè)數(shù)據(jù)的編號(hào)除以數(shù)據(jù)總數(shù)加1(即累積概率，cumulative probability)為縱坐標(biāo)作圖，用Origin 8.5擬合六價(jià)鉻的急性物種敏感度分布曲線(圖1)，擬合較好的是BiDoseResp函數(shù)，結(jié)果見表5，擬合公式為：

(5)

式中，y為累積概率，x為六價(jià)鉻濃度(μg·L-1)的對(duì)數(shù)值，A1、A2、p、LOGx1、LOGx2、h1及h2均為曲線特征參數(shù)。HC5=45.69 μg·L-1, CMC= HC5/ 2=22.84 μg·L-1。

用SSD法推導(dǎo)CCC時(shí)，采用同樣的方法擬合六價(jià)鉻的慢性物種敏感度分布曲線(圖2)，擬合較好的是Polynomial函數(shù)，結(jié)果見表5，擬合公式為：

y=A0+A1x+A2x2+A3x3+A4x5+A5x5

(6)

式中，y為累積概率，x為六價(jià)鉻濃度(μg·L-1)的對(duì)數(shù)值，A0、A1、A2、A3、A4、A5均為曲線特征參數(shù)。CCC=HC5=10.35 μg·L-1。

2.2.3 澳大利亞/新西蘭SSD法

采用Burr Ⅲ型分布作為SSD的擬合曲線，Burr Ⅲ型分布是一種靈活的分布函數(shù)，對(duì)物種敏感性數(shù)據(jù)擬合特性較好，在澳大利亞和新西蘭的環(huán)境風(fēng)險(xiǎn)評(píng)價(jià)和環(huán)境質(zhì)量標(biāo)準(zhǔn)制定中被推薦使用[20]，澳大利亞聯(lián)邦科學(xué)與工業(yè)研究組織(CSIRO)提供了該方法的說明和相關(guān)支持軟件BurrlizO(版本1.0.14)[92]。Burr Ⅲ型函數(shù)的參數(shù)方程：

(7)

圖1 六價(jià)鉻急性毒性數(shù)據(jù)擬合出的急性物種敏感度分布曲線注：SMAV為種急性毒性平均值，單位是μg·L-1。Fig. 1 The species sensitivity distribution curve based on acute toxicity data of hexavalent chromiumNote: SMAV is species mean acute value. Unit is μg·L-1.

圖2 六價(jià)鉻慢性毒性數(shù)據(jù)擬合出的慢性物種敏感度分布曲線注：SMCV為種慢性毒性平均值，單位是μg·L-1。Fig. 2 The species sensitivity distribution curve based on chronic toxicity data of hexavalent chromiumNote: SMCV is species mean chronic value. Unit is μg·L-1.

表5 物種敏感度分布(SSD)法對(duì)六價(jià)鉻急慢性毒性數(shù)據(jù)擬合結(jié)果Table 5 Fitted values of acute and chronic toxicity of hexavalent chromium by species sensitivity distribution method

注：CMC為基準(zhǔn)最大濃度；CCC為基準(zhǔn)連續(xù)濃度，HC5。

Note: CMC is criteria maximum concentration; CCC is criteria continuous concentration; HC5.

式中b、c、k為函數(shù)的3個(gè)參數(shù)。當(dāng)k趨于無窮大時(shí)，Burr Ⅲ型分布可變化為ReWeibull分布：

(8)

式中a、b為函數(shù)的2個(gè)參數(shù)。

當(dāng)c趨于無窮大時(shí)，可變化為RePareto分布：

(9)

式中x0、θ為函數(shù)的2個(gè)參數(shù)。

實(shí)際應(yīng)用中，如果k值大于100，就可以重新應(yīng)用ReWeibull分布函數(shù)擬合；當(dāng)c值大于80，就可以用RePareto分布函數(shù)擬合。對(duì)表1數(shù)據(jù)的對(duì)數(shù)值進(jìn)行擬合，符合RePareto分布，x0=5.3218，θ=2.7135，HC5=58.13 μg·L-1，CMC=HC5/2=29.06 μg·L-1；對(duì)表2數(shù)據(jù)的對(duì)數(shù)值進(jìn)行擬合，符合Burr Ⅲ分布，b=4.2864，c=16.9631，k=0.1176，CCC=HC5=9.00 μg·L-1。

3 討論(Discussion)

由于一個(gè)毒性數(shù)據(jù)集的分布不能完全吻合某種數(shù)理統(tǒng)計(jì)分布，所以選用的擬合函數(shù)不同，得出的水質(zhì)基準(zhǔn)值也不盡相同。利用3種方法對(duì)六價(jià)鉻水質(zhì)基準(zhǔn)推導(dǎo)值和已有研究的基準(zhǔn)值及美國(guó)的基準(zhǔn)值進(jìn)行比較(表6)。本研究3種方法推導(dǎo)出來的基準(zhǔn)值在一個(gè)數(shù)量級(jí)上，使用SSR法推導(dǎo)的中國(guó)的Cr(Ⅵ)基準(zhǔn)CMC值與CCC值均大于美國(guó)的基準(zhǔn)值，這可能是生物區(qū)系差異造成的。在本研究中，剔除了一些非中國(guó)物種的數(shù)據(jù)，如美國(guó)旗魚黑頭軟口鰷、斑馬魚、白鮭和美白鯉等，主要采用中國(guó)本土水生生物，另外還包含了一些中國(guó)引進(jìn)的物種，如虹鱒魚、尼羅羅非魚和太陽(yáng)魚等。

表6 六價(jià)鉻基準(zhǔn)值與水質(zhì)標(biāo)準(zhǔn)的比較Table 6 Comparison among criteria and standard values of hexavalent chromium

吳豐昌等[9]對(duì)運(yùn)用SSD法對(duì)多種重金屬進(jìn)行了基準(zhǔn)值推導(dǎo)，包括Cr(VI)，比較發(fā)現(xiàn)，其CMC值是本研究推導(dǎo)的CMC值的2倍，CCC值差異不大。其原因可能是本研究側(cè)重于收集自然水體中存在的生物，使2種研究的急慢性數(shù)據(jù)數(shù)不同；另外2種研究所用的SSD法擬合函數(shù)不一樣，擬合出來的結(jié)果也不同，進(jìn)而導(dǎo)致了基準(zhǔn)值的差異性。而本研究所用的SSR法主要考慮累積概率接近0.05的4個(gè)屬的毒性數(shù)據(jù)，區(qū)別于SSD法推導(dǎo)的基準(zhǔn)值。

運(yùn)用3種方法對(duì)六價(jià)鉻基準(zhǔn)進(jìn)行CMC值推導(dǎo)，SSR法主要考慮最敏感的4個(gè)屬，SSD法更具代表性，用BiDoseResp函數(shù)擬合得到的CMC值最小，相對(duì)比較嚴(yán)謹(jǐn)，BiDoseResp函數(shù)擬合優(yōu)度高達(dá)0.995，建議選擇該函數(shù)推導(dǎo)的CMC值；利用3種方法對(duì)六價(jià)鉻基準(zhǔn)進(jìn)行CCC值推導(dǎo)時(shí)，澳大利亞/新西蘭SSD法推導(dǎo)的CCC值最小，而SSD法運(yùn)用的Polynomial函數(shù)擬合優(yōu)度達(dá)到0.952，雖然SSD法沒有考慮污染物在生物體內(nèi)的富集效應(yīng)，但是相對(duì)SSR法推導(dǎo)的值，SSD法推導(dǎo)的CCC值相對(duì)比較保守，這樣的CCC值對(duì)水生物保護(hù)有利。因此，建議選擇SSD法推導(dǎo)六價(jià)鉻的急慢性基準(zhǔn)值。

3種方法得到的六價(jià)鉻水生生物基準(zhǔn)值與我國(guó)地表水環(huán)境質(zhì)量標(biāo)準(zhǔn)I級(jí)標(biāo)準(zhǔn)值相比較，在同一數(shù)量級(jí)上，CMC值均高于標(biāo)準(zhǔn)值，澳大利亞/新西蘭SSD法推導(dǎo)的CCC稍低于標(biāo)準(zhǔn)值，SSD法和SSR法推導(dǎo)的CCC值稍高于標(biāo)準(zhǔn)值。因目前我國(guó)的I級(jí)標(biāo)準(zhǔn)值為單值標(biāo)準(zhǔn)，其介于CMC與CCC之間，還是基本上能滿足對(duì)環(huán)境水體中短期應(yīng)急和長(zhǎng)期生物效應(yīng)的保護(hù)需求。不過考慮到水質(zhì)標(biāo)準(zhǔn)是在水質(zhì)基準(zhǔn)基礎(chǔ)上建立的，因此建議相關(guān)部門制定標(biāo)準(zhǔn)時(shí)可以考慮分別制定短期標(biāo)準(zhǔn)和長(zhǎng)期標(biāo)準(zhǔn)[5,93]。

我國(guó)幅員遼闊，不同流域或區(qū)域水生生物的種群和數(shù)量是不同的，水環(huán)境生態(tài)特征、水環(huán)境承載力等也都有很大的差異。針對(duì)我國(guó)這種不同區(qū)域的生物差異性明顯的特點(diǎn)，僅僅制定國(guó)家尺度的水質(zhì)基準(zhǔn)，對(duì)特定水體區(qū)域的生物，尤其是一些敏感水生生物提供的保護(hù)可能會(huì)不足，這就要求我們?cè)跇?gòu)建水質(zhì)基準(zhǔn)體系時(shí)，考慮到不同地域的物種差異性，也就是生態(tài)分區(qū)差異性，加強(qiáng)區(qū)域性敏感物種的水生生物毒性研究，豐富我國(guó)水生生物毒性數(shù)據(jù)庫(kù)，在制定國(guó)家基準(zhǔn)的同時(shí)還可制定流域尺度的水質(zhì)基準(zhǔn)。

綜上所述，本文的主要結(jié)論包括：

本研究采用已有水生生物毒性數(shù)據(jù)，結(jié)合本課題組實(shí)驗(yàn)數(shù)據(jù)，運(yùn)用SSR法、SSD法和澳大利亞SSD法推導(dǎo)出來的CMC值分別為23.97、22.84、29.06 μg·L-1，CCC值分別為14.63、10.35、9.00 μg·L-1。

比較這3種方法，建議使用SSD法推導(dǎo)六價(jià)鉻的CMC值和CCC值。

3種方法推導(dǎo)的六價(jià)鉻水生生物基準(zhǔn)值與我國(guó)地表水環(huán)境質(zhì)量標(biāo)準(zhǔn)I級(jí)標(biāo)準(zhǔn)值在同一個(gè)數(shù)量級(jí)上，我國(guó)的I級(jí)標(biāo)準(zhǔn)值為單值標(biāo)準(zhǔn)，其介于CMC與CCC之間，目前還是基本上能滿足對(duì)環(huán)境水體中短期應(yīng)急和長(zhǎng)期生物效應(yīng)保護(hù)的需求，但長(zhǎng)遠(yuǎn)來看，還是建立雙值標(biāo)準(zhǔn)為宜。

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◆

DerivationofFreshwaterQualityCriteriaforHexavalentChromiumforProtectionofAquaticOrganismsinChina

Liao Jing1, Liang Feng2, Yang Shaogui1, He Huan1, Sun Cheng1,*, Gao Shixiang1, Cui Yibin1

1. School of the Environment, Nanjing University, Nanjing 210023, China 2. Henan University of Urban Construction, Pingdingshan 467036, China

18 October 2013accepted19 December 2013

According to the methods and procedures of surface water qua1ity criteria established by United States Environmental Protection Agency (USEPA) (Guidelines for Deriving Numerical National Water Quality Criteria for the Protection of Aquatic Organisms and Their Uses, 1985), the aquatic species existing widely in China were selected, and their toxicity data were collected from database and acquired from our research on some native species. The aquatic quality criteria of hexavalent chromium in China were derived using three methods: species sensitivity rank (SSR), species sensitivity distribution (SSD) and the method of criteria development recommended by Australia. Results showed that the criteria maximum concentration (CMC) value of hexavalent chromium were 23.97, 22.84, 29.06 μg·L-1and the criteria continuous concentration (CCC) value were 14.63, 10.35, 9.00 μg·L-1, respectively. The criteria values were of the same order of magnitude. The criteria proposed in this study had a little difference from the criteria launched by USEPA. We suggest using SSD method to derive CMC value and CCC value. The results of this study might provide some useful clues and data for the development of China’s water quality criteria.

hexavalent chromium; freshwater aquatic organisms; water quality criteria; criteria maximum concentration (CMC); criteria continuous concentration (CCC)

國(guó)家水體污染控制與治理科技重大專項(xiàng)(2012ZX07501-003-002)；河南城建學(xué)院博士科研啟動(dòng)基金項(xiàng)目(2013JBS003)

廖靜(1989-)，女，碩士，研究方向?yàn)橹亟饘偎|(zhì)基準(zhǔn)，E-mail: june.0000@163.com；

*通訊作者(Corresponding author)，E-mail: envidean@nju.edu.cn

10.7524/AJE.1673-5897.20131018001

廖靜，梁峰，楊紹貴, 等. 我國(guó)六價(jià)鉻淡水水生生物安全基準(zhǔn)推導(dǎo)研究[J]. 生態(tài)毒理學(xué)報(bào), 2014, 9(2): 306-318

Liao J, Liang F, Yang S G, et al. Derivation of freshwater quality criteria for hexavalent chromium for protection of aquatic organisms in China [J]. Asian Journal of Ecotoxicology, 2014, 9(2): 306-318 (in Chinese)

2013-10-18錄用日期2013-12-19

1673-5897(2014)2-306-13

X171.5

A

孫成(1955—)，男，教授，博士生導(dǎo)師，主要從事微量與痕量有機(jī)污染物的分析、污染物的環(huán)境行為以及水體中有毒有機(jī)物去除技術(shù)與機(jī)理研究，發(fā)表科學(xué)論文140多篇。