Catalytic remediation of polycyclic aromatic hydrocarbons contaminated soil by synthetic siderite and its derivatives

doi:10.16085/j.issn.1000-6613.2023-0935

Abstract

Abstract:

To investigate the effects of different oxidation systems and operating parameters on the degradation performance of soil PAHs, synthetic siderite (SFC) was artificially simulated and modified siderite (FFC) was obtained by introducing nZVI with excellent performance to catalyze the oxidative degradation of PAHs in actual contaminated site soil. The results showed that both SFC and FFC-catalyzed PDS systems were effective in degrading PAHs, and the soil PAHs degradation rate was further improved by optimizing the operating parameters, including lowering the initial pH, increasing the soil-to-water ratio and extending the reaction time. In addition, the use of H₂O₂ equivalent instead of PDS could reduce the treatment cost, but the degradation rate was slightly decreased. The results of soil toxicity assessment showed that the germination rate of ryegrass seeds was significantly increased after SFC/PDS and FFC/PDS treatments. The study indicated that SFC and FFC catalytic systems could effectively remediate PAHs-contaminated soil and reduce soil ecotoxicity.

Key words: siderite, polycyclic aromatic hydrocarbons, catalysis, contaminated sites, in-situ chemical oxidation

摘要：

为考察不同氧化体系及运行参数对土壤多环芳烃降解性能的影响，本文通过人工仿真合成菱铁矿（SFC）并进一步引入纳米零价铁（nZVI）制备改性菱铁矿（FFC），催化氧化修复实际多环芳烃（PAHs）污染场地土壤。实验结果表明，SFC和FFC催化过硫酸钠（PDS）体系均能有效降解PAHs。通过优化运行参数包括降低初始pH、提高土水比和延长反应时间等可进一步提高土壤PAHs降解率。而等价处理实验结果显示，采用H₂O₂等价代替PDS虽可以降低治理成本，但PAHs降解率却有所下降。同时，土壤毒性评估结果发现经SFC/PDS和FFC/PDS处理后的黑麦草种子发芽率得到显著提高。本研究表明SFC和FFC催化体系可有效修复PAHs污染土壤，并缓减土壤生态毒性。

关键词: 菱铁矿, 多环芳烃, 催化, 污染场地, 原位化学氧化

CLC Number:

YANG Xin, ZHONG Chengwei, YANG Zhishan, ZHU Weiwei, WANG Wenhao, YU Jiang. Catalytic remediation of polycyclic aromatic hydrocarbons contaminated soil by synthetic siderite and its derivatives[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 4118-4127.

杨昕, 钟承韡, 杨志山, 朱韦韦, 王文浩, 余江. 人工仿真菱铁矿及其衍生材料催化修复PAHs污染土壤[J]. 化工进展, 2024, 43(7): 4118-4127.

Figures/Tables 11

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PAHs	污染物	环数	浓度/mg·kg^-1	占比/%	一类用地筛选值/mg·kg^-1	超标倍数
L-PAHs	萘（ANP）	2	1.12	0.55	25	—
	苊烯（ANY）	3	1.37	0.67	—	—
	苊（ANA）	3	未检出	0	—	—
	芴（FLU）	3	1.15	0.57	—	—
	菲（PHE）	3	20.16	9.91	—	—
	蒽（ANT）	3	8.40	4.13	—	—
M-PAHs	荧蒽（FLT）	4	25.24	12.40	—	—
	芘（PYR）	4	25.11	12.34	—	—
	苯并(a)蒽（BaA）	4	19.75	9.71	5.5	3.59
	䓛（CHR）	4	14.56	7.16	490	—
H-PAHs	苯并(b)荧蒽（BaE）	5	22.71	11.16	5.5	4.13
	苯并(k)荧蒽（BKF）	5	15.61	7.67	55	—
	苯并(a)芘（BaP）	5	22.84	11.23	0.55	41.53
	茚并(1.2.3-c,d)芘（IPY）	6	12.34	6.06	5.5	2.24
	二苯并(a,h)蒽（DBA）	6	1.99	0.98	0.55	3.62
	苯并(g,h,i)苝（BPE）	6	11.12	5.47	5.5	—
TPAH			203.47	100

PAHs	污染物	环数	浓度/mg·kg^-1	占比/%	一类用地筛选值/mg·kg^-1	超标倍数
L-PAHs	萘（ANP）	2	1.12	0.55	25	—
	苊烯（ANY）	3	1.37	0.67	—	—
	苊（ANA）	3	未检出	0	—	—
	芴（FLU）	3	1.15	0.57	—	—
	菲（PHE）	3	20.16	9.91	—	—
	蒽（ANT）	3	8.40	4.13	—	—
M-PAHs	荧蒽（FLT）	4	25.24	12.40	—	—
	芘（PYR）	4	25.11	12.34	—	—
	苯并(a)蒽（BaA）	4	19.75	9.71	5.5	3.59
	䓛（CHR）	4	14.56	7.16	490	—
H-PAHs	苯并(b)荧蒽（BaE）	5	22.71	11.16	5.5	4.13
	苯并(k)荧蒽（BKF）	5	15.61	7.67	55	—
	苯并(a)芘（BaP）	5	22.84	11.23	0.55	41.53
	茚并(1.2.3-c,d)芘（IPY）	6	12.34	6.06	5.5	2.24
	二苯并(a,h)蒽（DBA）	6	1.99	0.98	0.55	3.62
	苯并(g,h,i)苝（BPE）	6	11.12	5.47	5.5	—
TPAH			203.47	100

PAHs	初始pH		土水比		反应时间
PAHs	R值	P值	R值	P值	R值	P值
TPAH	-0.214	0.231	0.172	0.338	0.700^②	0.000
L-PAHs	-0.096	0.596	0.344	0.050	0.641^②	0.000
M-PAHs	-0.130	0.472	0.155	0.390	0.588^②	0.000
H-PAHs	-0.266	0.134	0.353	0.044^①	0.463^②	0.007

PAHs	初始pH		土水比		反应时间
PAHs	R值	P值	R值	P值	R值	P值
TPAH	-0.214	0.231	0.172	0.338	0.700^②	0.000
L-PAHs	-0.096	0.596	0.344	0.050	0.641^②	0.000
M-PAHs	-0.130	0.472	0.155	0.390	0.588^②	0.000
H-PAHs	-0.266	0.134	0.353	0.044^①	0.463^②	0.007

PAHs	TPAH		L-PAHs		M-PAHs		H-PAHs
PAHs	R值	P值	R值	P值	R值	P值	R值	P值
TPAH	1	—	0.748^②	0.000	0.790^②	0.000	0.854^②	0.000
L-PAHs	0.748^②	0.000	1	—	0.333	0.059	0.660^②	0.000
M-PAHs	0.790^②	0.000	0.333	0.059	1	—	0.433^①	0.012
H-PAHs	0.854^②	0.000	0.660^②	0.000	0.433^①	0.012	1	—