Overview
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Key numbers
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- other forums is permitted, provided the pattern. This decoupling, driven by differential rain-washing dynamics (24.5% As
- loss vs. 13.5% P loss), created unique selective pressure that drove co-enrich-
- 18%–27% of total arsenic in stormwater runoff provided direct evidence of active
- mechanisms, leading to the expectation that their distributions exposure: Industrial-High (IH, n = 3), Industrial-Low (IL, n = 3),
- should be positively correlated (Zhao et al., 2010). However, urban Traffic-High (TH, n = 3), Traffic-Low (TL, n = 3), Control-Campus
- interfaces present unique conditions where anthropogenic As (CC, n = 3), and Control-Gulangyu (CG, n = 3). All samples were col-
- arsenic transformation pathways have not been previously Supplementary Table S1.
- Cbefore × 100%, where Cbefore and Cafter represent total element concen- relation across the 18 urban interface samples (r = −0.76, p < 0.001;
- values are means across four rain events per site. (322 ± 71 mg kg−1), whereas control sites showed the opposite pat-
- DNA was extracted using the DNeasy PowerSoil Pro Kit (Qiagen). tern (CC: As = 7.0 ± 2.5 mg kg−1, p = 1,027 ± 154 mg kg−1; Table 1).
- are provided in Supplementary Table S4. transporter gene (pstS) showed parallel enrichment patterns across
- 2.3 Greenhouse gas production potential control sites (Figure 2a; Table 1). In contrast, the alkaline phosphatase
- Microcosm incubations were conducted following Angel et al. at P-rich control sites (Table 1). Notably, arsM and pstS abundances
- 120-mL serum bottles. Headspace was flushed with N2 (99.999%) for affinity phosphate uptake under dual As-P stress. The correlation
- 5 min and bottles were sealed with butyl rubber stoppers and alumi- matrix (Supplementary Table S3; Supplementary Figure S1) revealed
- Supplementary Section S4. arsenic (Figure 3; Table 2). Total As in runoff ranged from
- methylated arsenic species (MMA + DMA) comprised 18–27% of
- Statistical analyses were performed in R v4.3.1 (R Core Team, total runoff As across all groups (Figure 3b; Table 2), providing direct
- the shaded area indicating 95% confidence interval. (b) Box plots of As/P molar ratio across interface groups displayed on a logarithmic scale,
- demonstrating approximately 50-fold gradient from industrial-high to control sites. (c) Comparison of mean As (red bars) and P (blue bars, scaled ×10)
- Traffic-Low; CC, Control-Campus; CG, Control-Gulangyu. Statistical analysis of correlations is presented in Supplementary Table S3.
- TABLE 1 Physicochemical and microbial characteristics across urban interface types.
- Values are mean ± SD. Functional gene abundances are expressed as log10 copies g−1 dry weight.
- dynamics for As and P (Figure 4). Both elements decreased following PCA captured 77.3% of total variance in the first two axes
- rain events, but As showed consistently higher proportional losses (Figure 5; Supplementary Figure S1). PC1 (66.1%) clearly separated
- than P across all interface types (Figures 4a,b). At IH sites, mean As samples along the As-P gradient, with IH and IL sites clustering in the
- loss reached 24.5% compared to only 13.5% P loss (Figure 4c). This positive region associated with high As concentrations and elevated
- percentage in runoff. Data represent four rain events (n = 12 per group). Different lowercase letters indicate significant differences among groups (one-
- TABLE 2 Arsenic speciation and methylation potential in stormwater runoff.
- Values are mean ± SD from 4 rain events (n = 12 per group). MMA, monomethylarsonic acid; DMA, dimethylarsinic acid; Methylated As, MMA + DMA.
- Arsenic shows consistently higher loss rates than phosphorus, especially at industrial sites (IH: 24.5% vs. 13.5%), contributing to progressive As-P
- with arsC and arsM abundances slightly elevated during the wet was precluded by limited replication (n = 3). Leave-one-out analysis
- Supplementary Table S2). The pstS gene exhibited relatively stable r = 0.95. Although no formal multiple-testing correction was applied
- abundance (r = 0.98; Table 3). Interestingly, CO2 flux showed an
- nic transformation genes (Table 3). Both mcrA (r = 0.99, p < 0.001) gesting that high As levels may shift microbial carbon metabolism
- loadings. PC1 (66.1%) and PC2 (11.2%) together explain 77.3% of total variance. Red arrows indicate As-related variables (As, arsC, arsM, pstS); blue
- coefficients supporting this ordination are provided in Supplementary Table S3.
- Supplementary Table S3). Observed ASVs showed a similar pattern independently of phosphorus inputs derived mainly from biologi-
- pared to phosphorus during rain events (24.5% vs. 13.5% at industrial
- Top color bars indicate gene function category: As-related (red) or P-related (blue). Error bars represent standard error of the mean (n = 3 per group).
- Asterisks denote significant seasonal differences within each group (paired t-test; *p < 0.05, **p < 0.01, ns = not significant; n = 3). Seasonal data are
- TABLE 3 Anaerobic carbon metabolism potential and greenhouse gas-related gene abundances across urban interface types.
Methods (brief)
- cited, in accordance with accepted genes (r = 0.88, p < 0.001). Methylated arsenic species (MMA + DMA) comprising
- methylarsonic acid (MMA) and dimethylarsinic acid (DMA), thereby 2 Materials and methods
- Zhu et al., 2014). The arsM gene is widely distributed among bacteria 2.1 Study area, sampling design and sample
- interfaces present unique conditions where anthropogenic As (CC, n = 3), and Control-Gulangyu (CG, n = 3). All samples were col-
- explored. Surface biofilm samples were collected during the wet season
- 2006; Wang et al., 2015). Recent studies on paddy soils and con- collected within 24 h before and 24–48 h after the event from adjacent,
- iron/manganese can simultaneously suppress arsenic release and ing a disturbed surface. Stormwater runoff (500 mL) was collected
- reduce GHG emissions (Chen Y. et al., 2025; Chen et al., 2025a; Zhao from the base of sampled interfaces during each event. All samples
- et al., 1998). Whether urban interface biofilms harbor conditions Total As was determined by ICP-MS (Agilent 7,700x) after
- favorable for both arsenic methylation and anaerobic carbon metabo- HNO₃–HF-HClO₄ digestion (Huang et al., 2018). Total P was mea-
- in runoff (As(III), As(V), MMA, DMA) was determined by HPLC- the positive As-P correlation expected from shared geochemical
- ICP-MS (Gong et al., 2020). Phosphorus fractions (SRP, IP, OP) were behavior in natural systems. This decoupling is further reinforced
- Cbefore × 100%, where Cbefore and Cafter represent total element concen- relation across the 18 urban interface samples (r = −0.76, p < 0.001;
- trations (mg kg−1 dry weight) in biofilm samples collected from adja- Figure 1a; Supplementary Table S3). IH sites contained the highest
- was collected. Detailed incubation protocols are provided in Runoff samples revealed substantial microbial transformation of
- methylated arsenic species (MMA + DMA) comprised 18–27% of
- (As) and total phosphorus (P) concentrations across 18 urban interface samples. The solid line represents linear regression (r = −0.76, p < 0.001), with
- than P across all interface types (Figures 4a,b). At IH sites, mean As samples along the As-P gradient, with IH and IL sites clustering in the
Implications
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Update history
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