Determination of Dechlorane Plus Compounds in Complex Matrix Sludge by GC-MS/MS with Microwave-Assisted Extraction and Evaluation of Treatment Efficiency
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摘要:
德克隆类物质在污泥样品中以痕量水平(ng/g级)存在，加之污泥基质复杂，对污泥中德克隆类化合物的分析带来极大挑战。鉴于此，本文建立了微波辅助提取与气相色谱-三重四极杆串联质谱(GC-MS/MS)相结合，测定污水处理厂底泥中德克隆类化合物的分析方法。底泥样品采用微波辅助提取在线净化的方法，以丙酮-正己烷(1∶1，V/V)作为提取溶剂，在120℃温度和1500W功率条件下，该方法能够高效地从基质复杂的底泥样品中提取出德克隆类化合物，提取回收率超过80%。样品提取后，利用石墨化碳黑(GCB)和乙二胺基-N-丙基(PSA)固相萃取柱进一步净化，可有效地去除色素、脂类和非极性干扰物，减少基质干扰。借助质谱多反应监测(MRM)模式，针对目标化合物的特定离子对进行选择性监测，排除其他干扰离子的影响，从而实现了对德克隆类化合物的准确定量。该方法在5～400ng/mL浓度范围内线性关系良好，相关系数(r)不小于0.998，检出限为0.017～0.040ng/g。在低、中、高三个浓度水平底泥基质中，德克隆类化合物的平均回收率分别为79.8%～99.5%、86.2%～104.8%、91.2%～106.1%，相对标准偏差(RSD)＜7%。将该方法应用于实际底泥样品的检测，在11个污水处理厂底泥中均检出德克隆类化合物，且含量较高(31.4～195.6ng/g)。底泥中顺式德克隆(syn-DP)异构体比例的平均值fsyn=0.27，低于德克隆(DP)产品的fsyn值，这是由于底泥对反式德克隆(anti-DP)的吸附性更强，或底泥中的顺式德克隆(syn-DP)优先发生了生物降解。初步比较了11个污水处理厂采用不同的污水处理工艺处理底泥中德克隆化合物的效果，与活性污泥法水处理相比，采用A2/O工艺处理的德克隆类化合物的浓度显著降低，fsyn值显著增高，但其影响机制仍待深入探究。
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关键词:
- 德克隆化合物 /
- 污泥 /
- 微波辅助提取 /
- 气相色谱-三重四极杆串联质谱法 /
- 污水处理厂 /
- 顺式德克隆(syn-DP)异构体比例(fsyn)
Abstract:Dechlorane plus compounds are present at trace levels (ng/g) in sludge samples. The complex sludge matrix poses a significant challenge for the analysis of these compounds. To address this issue, we established an analytical method for determining dechlorane plus compounds in the sludge of sewage treatment plants, combining microwave-assisted extraction with gas chromatography-triple quadrupole tandem mass spectrometry. Sludge samples were processed using microwave-assisted extraction with online purification, and using acetone-n-hexane (1∶1, V/V) as the extraction solvent. After extraction, GCB/PSA solid-phase extraction columns were used for further purification to reduce matrix interference. The multiple reaction monitoring (MRM) mode of mass spectrometry was employed for accurate quantification. This method demonstrated good linearity (r≥0.998) in the 5−400ng/mL range, with a detection limit of 0.017−0.040ng/g. The average recoveries were 79.8%−99.5%, 86.2%−104.8% and 91.2%−106.1% at low, medium and high concentrations, respectively, with relative standard deviations (RSDs) of <7%. When applied to 11 sewage treatment plants, dechlorane plus compounds were detected, and the contents were relatively high (31.4−195.6ng/g). In sludge, average fsyn of syn-DP was 0.27, lower than that of DP products. This is due to stronger anti-DP adsorption or preferential syn-DP biodegradation. When the A2/O process was adopted, the concentration of dechlorane plus compounds was significantly reduced, and the fsyn value was significantly increased, but the influencing mechanism still needs to be further explored. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202409190197 . -
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表 1 德克隆类化合物的质谱分析参数
Table 1. Mass spectrometric analysis parameters of dechlorane plus and related compounds
序号
No.德克隆类化合物
Dechlorane plus and
related compounds保留时间
Retention time
(min)定量离子对
Quantitative ion pair定性离子对
Qualitative ion pairm/z CE(eV) m/z CE(eV) 1 Mirex 8.753 272.00＞236.80 15 274.00＞238.80 15 2 Dec602 10.028 272.00＞236.80 18 274.00＞238.90 18 3 13C12-PCB198 10.217 476.00＞405.70 39 474.00＞403.70 24 4 13C12-PCB209 10.678 510.00＞439.60 27 512.00＞439.90 33 5 Dec603 12.90 263.00＞192.90 30 261.00＞191.00 33 6 Dec604 13.258 420.00＞259.80 30 441.00＞281.00 36 7 anti-Cl10-DP 13.796 204.00＞168.90 18 202.00＞166.90 21 8 syn-DP 14.775 272.00＞236.80 15 274.00＞238.90 15 9 13C10-syn-DP 14.77 277.00＞241.80 18 278.85＞244.00 15 10 anti-Cl11-DP 15.027 238.00＞202.90 18 240.00＞204.90 18 11 anti-DP 15.262 272.00＞236.90 15 274.00＞238.80 15 12 13C10-anti-DP 15.259 277.00＞241.90 18 278.85＞243.90 15 
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表 2 德克隆类化合物的线性方程、相关系数、检出限和定量限
Table 2. Linear equations, correlation coefficients, detection limits and quantitation limits of dechlorane plus and related compounds
德克隆类化合物
Dechlorane plus and related compounds线性方程
Linear equation相关系数
Correlation coefficient (r)检出限
Detection limit (ng/g)Mirex y=0.2137x−2.3210 0.9995 0.024 Dec602 y=0.1604x−1.8138 0.9998 0.040 Dec603 y=0.0430x−0.7378 0.9988 0.024 Dec604 y=0.0024x+0.0073 0.9995 0.038 anti-Cl10DP y=0.1061x+1.8584 0.9993 0.017 syn-DP y=0.0190x+0.1920 0.9999 0.018 anti-Cl11DP y=0.1374x+3.1074 0.9987 0.040 anti-DP y=0.0491x+0.7488 0.9995 0.039
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表 3 德克隆类化合物的加标回收率和精密度
Table 3. Average recoveries and RSD of dechlorane plus and related compounds
德克隆类化合物
Dechlorane plus and
related compounds添加浓度2ng/g
Spiked concentration of 2ng/g添加浓度10ng/g
Spiked concentration of 10ng/g添加浓度30ng/g
Spiked concentration of 30ng/g平均回收率
Average recovery (%)RSD
(%)平均回收率
Average recovery (%)RSD
(%)平均回收率
Average recovery (%)RSD
(%)Mirex 89.8 6.29 93.3 5.58 106.0 2.79 Dec602 79.8 6.60 98.6 5.39 102.4 2.28 Dec603 92.5 2.28 104.8 3.73 91.2 3.70 Dec604 83.5 4.60 87.7 4.79 91.3 5.87 anti-Cl10DP 99.5 6.91 94.2 2.48 106.1 1.17 syn-DP 82.8 3.16 86.2 3.10 95.7 1.62 anti-Cl11DP 99.5 3.03 91.9 2.51 103.3 1.95 anti-DP 91.7 2.39 102.4 2.24 95.8 1.48 13C12-PCB209 88.3 4.12 102.3 3.28 100.8 2.97 13C10-syn-DP 94.8 3.56 92.2 3.16 85.9 2.31 13C10-anti-DP 89.5 2.89 94.9 2.39 91.4 3.56
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表 4 本文分析方法与相关文献分析方法的比较
Table 4. Comparison of the analytical methods in this paper and those in related literatures
目标物
Target compounds样品基质
Sample matrix样品前处理方法
Sample pretreatment method分析仪器Analytical instrument 方法回收率
Recovery of method方法检出限
Detection limit of method参考文献
Referencesyn-DP，anti-DP，
Dec602，Dec603，
Dec604干燥沉积物
Dry sediment索氏提取，多层硅胶柱净化
Soxhlet extraction，multi-layer silica
gel column purificationGC-HRMS 61%～106% 0.5～1pg/g ［33］ Mirex，syn-DP，anti-DP，
Dec602，Dec603，Dec604干燥沉积物和土壤
Dry sediment and soil加压液相萃取，镁铝层状双金属
氢氧化物净化
Pressure liquid phase extraction，Mg-Al
layered double oxides purificationGC-MS 90.3%～99.8% 0.01～0.67ng/g ［34］ Mirex，syn-DP，anti-DP，
Dec602，Dec603，
Dec604，anti-Cl10DP，
anti-Cl11DP新鲜底泥
Fresh sludge微波辅助提取，GCB/PSA固相萃取柱净化
Microwave assisted extraction，
GCB/PSA solid phase extraction
column purificationGC-MS/MS 79.8%～106.0% 0.017～0.040ng/g 本文研究
This study
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