Microbiologically influenced corrosion of Cu by nitrate reducing marine bacterium Pseudomonas aeruginosa

doi:10.1016/j.jmst.2020.02.008

Abstract

Abstract:

The microbiologically influenced corrosion (MIC) mechanisms of copper by Pseudomonas aeruginosa as a typical strain of nitrate reducing bacteria (NRB) was investigated in this lab study. Cu was immersed in deoxygenated LB-NO₃ seawater inoculated with P. aeruginosa and incubated for 2 weeks. Results showed that this NRB caused pitting and uniform corrosion. The maximum pit depths after 7 d and 14 d in 125 mL anaerobic vials with 50 mL broth were 5.1 μm and 9.1 μm, accompanied by specific weight losses of 1.3 mg/cm² (7 d) and 1.7 mg/cm² (14 d), respectively. Electrochemical measurements corroborated weight loss and pit depth data trends. Experimental results indicated that extracellular electron transfer for nitrate reduction was the main MIC mechanism and ammonia secreted by P. aeruginosa could also play a role in the overall Cu corrosion process.

Key words: Cu, Pseudomonas aeruginosa, Biofilm, Nitrate reducing bacteria, Microbiologically influenced corrosion, Pitting corrosion

Yanan Pu, Wenwen Dou, Tingyue Gu, Shiya Tang, Xiaomei Han, Shougang Chen. Microbiologically influenced corrosion of Cu by nitrate reducing marine bacterium Pseudomonas aeruginosa[J]. J. Mater. Sci. Technol., 2020, 47: 10-19.

Figures/Tables 20

Table 1 Experimental conditions for studying corrosion behavior of Cu induced by P. aeruginosa under anaerobic condition.

Parameter	Condition
P. aeruginosa	PAO1 strain
Culture medium	Tryptone 10 g
(LB-NO₃ medium)	Yeast extract 5 g
	NaCl 5 g
	KNO₃ 10 g
	Sterile seawater 1 L
Oxygen scavenger Temperature	100 ppm L-cysteine 37 ℃
Initial pH	7.2 ± 0.1
Incubation time	7 d, 14 d
Temperature	37 °C
Coupon material	Cu

Fig. 1. P. aeruginosa planktonic cell count (A) during the 14 d incubation, and sessile cell count (B) on Cu surface after 1, 3, 7 and 14 d incubation in 125 mL anaerobic vials with 50 mL broth.

Fig. 2. FM images of P. aeruginosa sessile cells on Cu coupons after 7 d incubation (A) and 14 d incubation (B) in anaerobic vials.

Fig. 3. SEM images of P. aeruginosa biofilms and corrosion products on Cu coupons after 7 d incubation (A), and after 14 d incubation (B) in anaerobic vials.

Fig. 4. High-resolution XPS spectra of C 1s (A), Ca 2p (B), Mg 1s (C), O 1s (D), N 1s (E) and Cu 2p (F) of Cu coupons after 14 d immersion in P. aeruginosa broth.

Table 2 Fitting parameters (valence state and binding energy of the elements, and the atomic percentage of each element) for C 1s, Ca 2p, Mg 1s, O 1s, N 1s and Cu 2p derived from XPS spectra in Fig. 4.

Valence state	Substrate	Binding energy (eV)	Proposed component	%
C 1 s	Cu	284.6 eV	C—C	79.28
		285.9 eV	C—O—C	15.59
		288.3 eV	CO₃^2-	5.13
Ca 2p	Cu	347.3 eV	CaCO₃	44.50
		351.1 eV	CaCO₃	55.50
Mg 1 s	Cu	1304.3 eV	MgCO₃	100
O 1 s	Cu	532.6 eV	OH^-	50.33
		531.7 eV	CO₃^2-	26.93
		533.0 eV	H₂O	17.81
		530.7 eV	O^2-	1.92
N 1 s	Cu	399.6 eV	NH₃	100
Cu 2p	Cu	932.8 eV	Cu₂O	73.06
		933.7 eV	CuO	26.94

Fig. 5. Culture medium pH and ammonia concentration in headspace during 14 d incubation with P. aeruginosa in anaerobic vial.

Table 3 [NH3] and [NH4+] in liquid phase after the 3 d, 7 d and 14 d incubation with P. aeruginosa.

Incubation (d)	[NH₃] in headspace (ppm) (v/v)	Total pressure in headspace (bar)	NH₃ partial pressure in headspace (bar)	[NH₃] in liquid phase (M)	[NH₄⁺] in liquid phase (M)
3	1.33	1.19	1.59 × 10^-6	2.75 × 10^-3	2.19 × 10^-4
7	1.97	1.43	2.81 × 10^-6	4.86 × 10^-3	2.91 × 10^-4
14	1.95	1.42	2.76 × 10^-6	4.78 × 10^-3	2.89 × 10^-4

Fig. 6. Weight losses of Cu coupons after 7 d and 14 d immersions in P. aeruginosa broth in anaerobic vials.

Fig. 7. Pit distributions on Cu coupons (after removing biofilms and corrosion products): (A) after immersion in abiotic control medium for 14 d, and in P. aeruginosa broth for 7 d (B) and 14 d (C) in anaerobic vials.

Fig. 8. 3D Pitting morphologies and maximum pit depths measured under CLSM on Cu coupons: after immersion in abiotic control medium for 14 d (A, A'), and in P. aeruginosa broth for 7 d (B, B') and 14 d (C, C') in anaerobic vials.

Fig. 9. OCP curves of Cu during 14 d immersion in abiotic control medium and in P. aeruginosa broth in 450 mL anaerobic vials with 200 mL culture medium.

Fig. 10. Rp curves of Cu during 14 d immersion in abiotic control medium and in P. aeruginosa broth.

Fig. 11. Nyquist and Bode plots of Cu during 14 d immersion in abiotic control medium (A, B) and in P. aeruginosa broth (C, D) (For comparation, the Nyquist and Bode plots of Cu after 14 d immersion in abiotic control medium is also showed in C and D).

Fig. 12. Equivalent electrical circuits used for fitting EIS spectra for Cu in abiotic control medium (A) and P. aeruginosa broth (B).

Table 4 EIS parameters for Cu immersed in abiotic culture medium in anaerobic glass cell.

Incubation (d)	R_s (Ω cm²)	Y_dl (Ω^-1 cm^-2 sⁿ)	n_dl	R_ct (kΩ cm²)
1	5.2	0.000082	0.85	53.7
3	6.3	0.000077	0.84	55.3
7	5.0	0.00012	0.82	58.8
14	6.4	0.000089	0.81	58.7

Table 5 EIS parameters for Cu immersed in culture medium inoculated with P. aeruginosa in anaerobic glass cell.

Incubation (d)	R_s (Ω cm²)	Y_b (Ω^-1 cm^-2sⁿ)	n_b	R_b (kΩ cm²)	Y_dl (Ω^-1 cm^-2 sⁿ)	n_dl	R_ct (kΩ cm²)
1	6.1	0.00018	0.90	2.4	0.00018	0.91	9.8
3	4.4	0.00033	0.78	10.6	0.00030	0.75	15.7
7	5.2	0.00017	0.74	3.5	0.00230	0.99	14.8
14	5.0	0.00037	0.77	12.8	0.00038	0.83	15.8

Fig. 13. Rb + Rct derived from EIS spectra.

Fig. 14. Tafel polarization curves of Cu after 7 d and 14 d immersions in abiotic control medium and in P. aeruginosa broth.

Table 6 Tafel parameters for Cu after incubation at 37 °C for 14 d.

Sample	i_corr (A cm^-2)	E_corr (V) vs. SCE	β_c (V dec^-1)
After 7 d in the abiotic medium	0.68 × 10^-7	-0.524	-0.148
After 14 d in the abiotic medium	0.53 × 10^-7	-0.485	-0.118
After 7 d in the P. aeruginosa broth	4.74 × 10^-7	-0.797	-0.228
After 14 d in the P. aeruginosa broth	0.89 × 10^-⁷	-0.704	-0.114

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