Mobility and sulfidization of heavy metals in sediments of a shallow eutrophic lake, Lake Taihu, China

The technique of DGT (diffusive gradients in thin films) using three diffusive gel thicknesses was applied to estimate the mobility and bioavailability of heavy metals in sediments and porewater of Lake Taihu, China. The DGT results showed significantly positive correlations between Co, Pb, Cd and Mn, and Ni and Fe concentrations in porewater. Cu and Zn showed a significantly negative correlation with Mn, due to Cu combination with carbonates and Zn derived from agricultural pollution, respectively. The rank order of average concentrations of Co, Ni and Cd at each station was DGT_1.92 > DGT_0.78 > DGT_0.39, suggesting stronger resupply from sediments to porewater when using thicker diffusive gels. Comparing centrifugation and DGT measurements, Co, Ni and Cd are highly labile; Mn and Fe are moderately labile; and Cu, Zn and Pb are slightly labile. The variations of AVS concentrations in sediment cores indicate that metal sulfides in deeper layers are easily diffused into surface sediments.     

红枫湖沉积物中重金属元素溯源分析的初步探讨

分析了红枫湖表层沉积物中有机质及10种重金属元素的含量,并应用平均富集因子(AEFs)对其污染状况进行了评价.结果表明,红枫湖表层沉积物的重金属按污染水平可分为3类:轻度污染(AEFs2)的Cd、Pb、Zn、Cr,As、Fe和Mn,中度污染(AEFs=2～3)的Cu,严重污染(AEFs3)的Ni和Hg.同时,通过主成分分析(PCA)法对影响湖泊沉积物中重金属分布的因素进行了分析,并在进行统计分析前,用Al对重金属元素含量进行了校正,以消除沉积物粒度对重金属分布的影响.分析结果表明,前3个主成分的贡献率分别为48.7%、20.5%、12.6%,所占比例总和大于80%,即这3个主成分基本能够代表原污染因素的大部分信息.结合湖泊特点及周边点源污染情况分析发现,红枫湖表层沉积物中重金属污染主要有3个可能来源:工业排污及Fe和Mn的影响;有机质的影响;早期岩石的风化及侵蚀(背景值).PCA聚类分析结果表明,本研究所调查的14个站位在污染程度上可分为4类,其结果反应出红枫湖沉积物中部分重金属、部分站位污染程度相对较重的特点,同时也进一步说明了工业排污是沉积物中重金属污染的主要来源.     

Historical trends of heavy metal contamination and their sources in lacustrine sediment from Xijiu Lake, Taihu Lake Catchment, China

Concentrations of Cd, Cr, Cu, Pb, Zn and Hg in Xijiu Lake sediment from the Taihu Lake catchment, China, were analyzed. Their contamination state was investigated based on the geoaccumulation index and enrichment factors. Statistical analysis was used to differentiate the anthropogenic versus natural sources of heavy metals (HMs), and the anthropogenic accumulation fluxes were calculated to quantify anthropogenic contribution to HMs. The results indicated that the lake sediment had been heavily contaminated by Cd, enrichment of Zn and Hg was at a relatively high level, while that of Cu and Pb was in the lower-to-moderate level and Cr was in the low enrichment level. Sources of Cr in the sediment were mainly from natural inputs, while other metals, especially Cd, were predominantly derived from anthropogenic sources. In the past century, anthropogenic accumulation fluxes of Pb, Zn and Hg increased by 0.1-47.3 mg/(cm².yr), 2.4-398.1 mg/(cm².yr), and 3.7-110.3 ng/(m².yr), respectively, accounting for most inputs of HMs entering the sediment. The contamination state of HMs varied with industrial development of the catchment, which demonstrated that contamination started in the early 20th century, reached the maximal level between the mid-1970s and mid-1990s, and decreased a little after the implementation of constraints on high contamination industries, although the contamination of some HMs, such as Cd, Zn and Hg, is still at high levels.     

Origins of black carbon from anthropogenic emissions and open biomass burning transported to Xishuangbanna, Southwest China

Black carbon (BC) has importance regarding aerosol composition, radiative balance, and human exposure. This study adopted a backward-trajectory approach to quantify the origins of BC from anthropogenic emissions ($\mathrm{B}{\mathrm{C}}_{\text{An}}$) and open biomass burning ($\mathrm{B}{\mathrm{C}}_{\text{BB}}$) transported to Xishuangbanna in 2017. Haze months, between haze and clean months, and clean months in Xishuangbanna were defined according to daily PM_2.5 concentrations of >75, 35–75, and <35 µg/m³, respectively. Results showed that the transport efficiency density (TED) of BC transported to Xishuangbanna was controlled by the prevailing winds in different seasons. The yearly contributions to the effective emission intensity of $\mathrm{B}{\mathrm{C}}_{\text{An}}$ and $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ transported to Xishuangbanna were 52% and 48%, respectively. However, when haze occurred in Xishuangbanna, the average $\mathrm{B}{\mathrm{C}}_{\text{An}}$ and $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ contributions were 23% and 77%, respectively. This suggests that open biomass burning (BB) becomes the dominant source in haze months. Myanmar, India, and Laos were the dominant source regions of BC transported to Xishuangbanna during haze months, accounting for 59%, 18%, and 13% of the total, respectively. Furthermore, India was identified as the most important source regions of $\mathrm{B}{\mathrm{C}}_{\text{An}}$ transported to Xishuangbanna in haze months, accounting for 14%. The two countries making the greatest contributions to $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ transported to Xishuangbanna were Myanmar and Laos in haze months, accounting for 55% and 13%, respectively. BC emissions from Xishuangbanna had minimal effects on the results of the present study. It is suggested that open BB in Myanmar and Laos, and anthropogenic emissions in India were responsible for poor air quality in Xishuangbanna.     

Chemical signature and fractionation of trace elements in fine particles from anthropogenic and natural sources

The health effects of trace metal elements in atmospheric fine particulate matter (PM_2.5) are widely recognized, however, the emission factor profiles and chemical fractionation of metal elements in different sources were poorly understand. In this study, sixteen metal elements, including Cd, Pb, V, Zn, Ba, Sb, As, Fe, Sr, Cr, Rb, Co, Mn, Cu, Ni and Sn from biomass burning, bituminite and anthracite combustion, as well as dust, were quantified. The results show different emission sources were associated with distinct emission profiles, holding important implications for source apportionment of ambient particulate metals. Specifically, Fe was the dominant metal species (28-1922 mg/kg) for all samples, and was followed by different metals for different samples. For dust, Mn (39.9 mg/kg_dust) had the second-highest emission factor, while for biomass burning, it was Cr and Ba (7.5 and 7.4 mg/kg_biomass, respectively). For bituminous coal combustion, the emission factor of Zn and Ba was 6.2 and 6.0 mg/kg_bituminous, respectively, while for anthracite combustion the corresponding emission factor was 5.6 and 4.3 mg/kg_anthracite, respectively. Moreover, chemical fractionation (i.e., the exchangeable, reducible fraction, oxidizable, and residual fraction) and the bioavailability index (BI) values of the metal elements from different sources were further investigated to reveal the link between different emission sources and the potential health risk. The findings from this study hold important implications for source apportionment and source-specific particulate metal-associated health effects.     

In-situ observations of internal dissolved heavy metal release in relation to sediment suspension in lake Taihu, China

Despite laboratory experiments that have been performed to study internal heavy metal release, our understanding of how heavy metals release in shallow eutrophic lakes remains limited for lacking in-situ evidence. This study used automatic environmental sensors and a water sampling system to conduct high-frequency in-situ observations(1-hr intervals) of water environmental variables and to collect water samples(3-hr intervals), with which to examine the release of internal heavy metals in Lake T...     

Bioaccumulation and human health risk assessment of trace metals in the freshwater mussel Cristaria plicata in Dongting Lake, China

Trace metal contamination in water and bioaccumulation in aquatic organisms are human health risks of increasing concern. However, the bioaccumulation of trace metals in the organs of the mussel Cristaria plicata in Dongting Lake, China and the human health risks of mussel consumption are largely unknown. We investigated the concentrations of 15 trace metals and metalloids in surface water, sediments, and C. plicata organs (foot, gill, mantle, and visceral mass) and quantified the bioaccumulation and human health risk of these trace metals in specimens collected from Dongting Lake. The concentrations of most metals in surface water exceeded previously published background values. In contrast, the concentrations of most metals in sediments showed a decreasing trend. Overall, the metal concentrations in the gill and visceral masses of C. plicata were higher than those in the foot and mantle, and higher bioaccumulation capacities were observed for essential metals than for nonessential metals. The mean concentrations of the trace elements Zn, Pb, Cd, As, Cu, and Cr in C. plicata foot samples were lower than the threshold values established by international and Chinese organizations. The estimated daily intake (EDI) values of the essential metal Mn in C. plicata foot was higher than the recommended tolerable daily intake (TDI) values for juveniles. Only Mn for juveniles and As for both juveniles and adults may pose noncarcinogenic health risks through foot consumption. The hazard index (HI) values for adults and juveniles were higher than 1, suggesting significant risks of noncarcinogenic effects to humans by exposure to multiple metals.     

Distribution and relationship between antimicrobial resistance genes and heavy metals in surface sediments of Taihu Lake, China

Heavy metals, pharmaceuticals, and other wastes released into the environment can significantly influence environmental antibiotic resistance. We investigated the occurrence of 22 antimicrobial resistance genes(ARGs) and 10 heavy metal concentrations, and the relationship between ARGs and heavy metals in surface sediment from seven sites of Lake Taihu. The results showed significant correlations(p 0.05) between sediment ARG levels,especially for tetracycline and sulfonamides(e.g., tet(A), tet(D), tet(E), tet(O), sul1, sul2 and int-1) and specific heavy metals(Fe, Mn, Cr, Cu, Zn, among others) in the Lake. In the surface sediments, heavy metals showed an interaction with resistance genes, but the strength of interaction was diminished with increasing depth. For most of the heavy metals, the concentration of elements in the top sediments was higher than that in other depths.Tetracycline resistance genes(tet(A), tet(B), tet(D), tet(E) and tet(O), β-lactam resistance genes(SHV, TEM, CTX, OXA and OXY) and sulfonamide resistance genes(sulA, sul1, sul2, sul3 and int-1) were detected. They showed a trend which inferred a statistically significant increase followed by decreases in the relative abundance of these ARGs(normalized to 16 S rRNA genes) with increasing depth. This study revealed that tet(A), tet(O), TEM, OXY, int-1, sul1 and sul3 were widespread in surface sediments with high abundance, indicating that these genes deserve more attention in future work.     

基于铅稳定同位素的骆马湖沉积物重金属铅来源解析

骆马湖作为南水北调东线工程重要的调蓄湖泊和水源地,其水环境安全对于江苏北部乃至南水北调东线工程的影响深远。通过对骆马湖湖区及入湖河段表层沉积物、湖周地区环境中潜在污染源土壤的Pb浓度和Pb同位素组成进行分析,评估Pb的空间分布;利用富集系数法进行Pb生态风险评价,结合二元线性混合模型进行湖区表层沉积物Pb来源解析,并计算各污染源的相对贡献率。结果表明：骆马湖表层沉积物中Pb浓度为8.09~27.97 mg/kg,平均值为20.94 mg/kg,Pb污染程度为清洁~轻度富集,表层沉积物Pb污染主要集中在东部和北部湖区;表层沉积物Pb同位素中²⁰⁶Pb/²⁰⁷Pb与²⁰⁸Pb/(²⁰⁶Pb+²⁰⁷Pb)（丰度之比）分别为1.170~1.249和1.125~1.131,Pb污染主要来源于老沂河和以渔业养殖为主的农业污染的直接排放,农业源的相对贡献率为46.71%。为防控骆马湖水环境中Pb的污染风险,需加强对渔业养殖的规范化管理和入湖河流的污染管控。

     

Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area

In order to understand the size distribution and the main kind of heavy metals in particulate matter on the lead and zinc smelting affected area, particulate matter(PM) and the source samples were collected in Zhuzhou, Hunan Province from December 2011 to January 2012 and the results were discussed and interpreted. Atmospheric particles were collected with different sizes by a cascade impactor. The concentrations of heavy metals in atmospheric particles of different sizes, collected from the air and from factories, were measured using an inductively coupled plasma mass spectrometry(ICP-MS). The results indicated that the average concentration of PM, chromium(Cr), arsenic(As), cadmium(Cd) and lead(Pb) in PM was177.3 ± 33.2 μg/m~3, 37.3 ± 8.8 ng/m~3, 17.3 ± 8.1 ng/m~3, 4.8 ± 3.1 ng/m~3 and 141.6 ± 49.1 ng/m~3,respectively. The size distribution of PM displayed a bimodal distribution; the maximum PM size distribution was at 1.1–2.1 μm, followed by 9–10 μm. The size distribution of As, Cd and Pb in PM was similar to the distribution of the PM mass, with peaks observed at the range of1.1–2.1 μm and 9–10 μm ranges while for Cr, only a single-mode at 4.7–5.8 μm was observed. PM(64.7%), As(72.5%), Cd(72.2%) and Pb(75.8%) were associated with the fine mode below 2.1 μm,respectively, while Cr(46.6%) was associated with the coarse mode. The size distribution characteristics, enrichment factor, correlation coefficient values, source information and the analysis of source samples showed that As, Cd and Pb in PM were the typical heavy metal in lead and zinc smelting affected areas, which originated mainly from lead and zinc smelting sources.     

Use of polymeric sub-micron ion-exchange resins for removal of lead, copper, zinc, and nickel from natural waters

This research investigated the removal capacity of polymeric sub-micron ion-exchange resins(SMR) for removal of lead, copper, zinc, and nickel from natural waters in competition with natural organic matter(NOM). Polymeric SMR particles were created and tested to ensure that they were adequately dispersed in the solution. They removed little NOM(10%or less) from river water and wastewater, indicating that competition from NOM was not a major concern. SMR were able to remove 82% ± 0.2% of lead, 46% ± 0.6% of copper, 55% ±20% of zinc, and 17% ± 2% of nickel from river water spiked with 500 μg/L of each. Similarly,in wastewater, they were able to remove 86% ± 0.1% of lead, 38% ± 0.8% of copper, 28% ± 1%of zinc, and 11% ± 1% of nickel.     

Bacterial community response to petroleum contamination in brackish tidal marsh sediments in the Yangtze River Estuary, China

The brackish tidal marsh in the Baimaosha area of the Yangtze River Estuary was severely contaminated by 400 tons of heavy crude petroleum from a tanker that sank in December 2012. The spill accident led to severe environmental damage owing to its high toxicity, persistence and wide distribution. Microbial communities play vital roles in petroleum degradation in marsh sediments. Therefore, taxonomic analysis, high-throughput sequencing and 16S rRNA functional prediction were used to analyze the structure and function of microbial communities among uncontaminated (CK), lightly polluted (LP), heavily polluted (HP), and treated (TD) sediments. The bacterial communities responded with increased richness and decreased diversity when exposed to petroleum contamination. The dominant class changed from Deltaproteobacteria to Gammaproteobacteria after petroleum contamination. The phylum Firmicutes increased dramatically in oil-enriched sediment by 75.78%, 346.19% and 267.26% in LP, HP and TD, respectively. One of the suspected oil-degrading genera, Dechloromonas, increased the most in oil-contaminated sediment, by 540.54%, 711.27% and 656.78% in LP, HP and TD, respectively. Spore protease, quinate dehydrogenase (quinone) and glutathione-independent formaldehyde dehydrogenase, three types of identified enzymes, increased enormously with the increasing petroleum concentration. In conclusion, petroleum contamination altered the community composition and microorganism structure, and promoted some bacteria to produce the corresponding degrading enzymes. Additionally, the suspected petroleum-degrading genera should be considered when restoring oil-contaminated sediment.     

Nano-selenium controlled cadmium accumulation and improved photosynthesis in indica rice cultivated in lead and cadmium combined paddy soils

Selenium nanoparticles (Se NPs) are less toxic and more biocompatible than selenite or selenate. However, studies involving spraying with Se NPs for reducing accumulation of cadmium (Cd) and lead (Pb) in rice grains have been rarely reported as yet. Herein, indica rice seedlings cultivated in Cd+Pb-spiked paddy soils (denoted as positive control) were sprayed with Se NPs sols for four times from tillering to booting stage. Compared to positive control, 50–100 μmol/L Se NPs downregulated Cd transporters-related genes such as OsLCT1, OsHMA2 and OsCCX2 in leaves and OsLCT1, OsPCR1 and OsCCX2 genes in node I at filling stage. Meanwhile, Se-binding protein 1 was distinctly elevated, involving the repression of Cd and Pb transportation to rice grains. Se NPs also differentially improved RuBP carboxylase and chlorophylls especially some key genes and proteins involving photosynthetic system. Besides, 25–50 μmol/L Se NPs diminished reactive oxygen species overproduction from NADPH oxidases whereas boosted glutathione peroxidase, reducing protein carbonylation in rice seedlings. However, the antioxidant isozymes and oxidatively modified proteins were slightly rebounded at 100 μmol/L. Se contents were noticeably elevated and confirmed to exist as selenomethionine in the rice grains following all the treatments by Se NPs. Thus, the optimal dosage of Se NPs for foliar application is 50 μmol/L, which significantly decreased Cd accumulation, improved photosynthesis and Se enrichment whereas caused no distinct reduction of Pb in the grains. Thus, an appropriate dosage of Se NPs can be conducted to decrease Cd accumulation, improve photosynthesis, and organic Se contents in rice grains.     

我国几个工矿与污灌区土壤重金属污染状况及原因探讨

对我国几个重工业区、矿区、开发区以及污灌区土壤重金属污染状况的调查结果表明，土壤重金属含量绝大部分高于土壤背景值，Cd、Zn等明显超标，某些重金属元素含量间还存在着一定的伴生规律。土中浸提态Cd、Zn含量与土壤pH值呈负相关。土壤中的重金属主要来自于污灌、金属矿藏开采、污泥利用以及大气飘尘等。金属冶炼厂附近土壤中Pb、Zn、Cd含量皆与离污染源距离呈密切的指数相关（R^2＞0.9）。     

Copper stimulates the incidence of antibiotic resistance, metal resistance and potential pathogens in the gut of black soldier fly larvae

The black soldier fly larvae (BSFL) have been successfully applied to treat various organic wastes. However, the impacts of heavy metals on antibiotic resistance in the BSFL guts are poorly understood. Here, we investigated the effect of copper (exposure concentrations of 0, 100 and 800 mg/kg) on the antibiotic and metal resistance profiles in BSFL guts. A total of 83 antibiotic resistance genes (ARGs), 18 mobile genetic elements (MGEs) and 6 metal resistance genes (MRGs) were observed in larval gut samples. Exposure to Cu remarkably reduced the diversity of ARGs and MGEs, but significantly enhanced the abundances of gut-associated ARGs and MRGs. The levels of MRGs copA, czcA and pbrT were dramatically strengthened after Cu exposure as compared with CK (increased by 2.8–13.5 times). Genera Enterococcus acted as the most predominant potential host of multiple ARG, MGE and MRG subtypes. Meanwhile, high exposure to Cu aggravated the enrichment of potential pathogens in BSFL guts, especially for Escherichia, Enterococcus and Salmonella species. The mantel test and procrustes analysis revealed that the gut microbial communities could be a key determinant for antibiotic and metal resistance. However, no significant positive links were observed between MGEs and ARGs or MRGs, possibly suggesting that MGEs did not play a crucial role in shaping the ARGs or MRGs in BSFL guts under the stress of Cu. These findings extend our understanding on the impact of heavy metals on the gut-associated antibiotic and metal resistome of BSFL.     

Trace metal dynamics in an industrialized Brazilian river: A combined application of Zn isotopes, geochemical partitioning, and multivariate statistics

The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ^66/64Zn_JMC ≈ + 0.30‰) and anthropogenic (δ^66/64Zn_JMC ≈ + 0.15‰) end members. The lighter δ^66/64Zn_JMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.     

A meta-analysis of heavy metals pollution in farmland and urban soils in China over the past 20 years

A total of 713 research papers about field monitor experiments of heavy metals in farmland and urban soils in China, published from 2000 to 2019, were obtained. A meta-analysis was conducted to evaluate the level of China's heavy metal pollution in soils, mainly focusing on eight heavy metals. It was found that the average concentrations of cadmium (Cd), lead (Pb), zinc (Zn), copper (Cu), mercury (Hg), chromium (Cr), nickel (Ni), and arsenic (As) in China were 0.19, 30.74, 85.86, 25.81, 0.074, 67.37, 27.77 and 8.89 mg/kg, respectively. Compared with the background value (0.097 mg/kg), the Cd content showed a twofold (0.19 mg/kg) rise in farmland soils and a threefold (0.29 mg/kg) rise in urban soils. The decreasing order of the mean I_geo was Cd (1.77) > Pb (0.62) > Zn (0.60) > Cu (0.58) > Hg (0.57) > Cr (0.54) > Ni (0.47) > As (0.28). Nearly 33.54% and 44.65% of sites in farmland and urban soils were polluted with Cd. The average concentrations of eight heavy metals were not sensitive change in recent two decades in farmland and urban soils. The average P_n values for urban (2.52) and farmland (2.15) soils showed that heavy metal pollution in urban soils was more serious than that in farmland, and the middle Yangtze River regions, where industrial activity dominates, were the most polluted. The meta-analysis comprehensively evaluated the current pollution situation of soil heavy metal, and provided important basis for soil management and environment prevention in China.     

Effect of struvite and organic acids on immobilization of copper and zinc in contaminated bio-retention filter media

Few studies have been carried out to connect nutrient recovery as struvite from wastewater and sustainable utilization of the recovered struvite for copper and zinc immobilization in contaminated soil. This study revealed the effect of struvite on Cu and Zn immobilization in contaminated bio-retention soil in the presence of commonly exuded plant organic acids. The research hypothesis was that the presence of both struvite and organic acids may influence the immobilization of Cu and Zn in soil. ...     

Distribution, risk and bioavailability of metals in sediments of Lake Yamdrok Basin on the Tibetan Plateau, China

Total contents of metals in soil and sediments on the Tibetan Plateau of China have been widely analyzed, but existing information is insufficient to effectively evaluate metal ecological risk because of a lack of metal bioavailability data. In this study, distribution, potential risk, mobility and bioavailability of metals in sediments of Lake Yamdrok Basin in Tibet of China were explored by combined use of total digestion, sequential extraction and the diffusive gradient in thin-films(DGT). Av...     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmospheric mixing ratios of carbonyl sulfide (COS) in Beijing were intensively measured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximum average value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations (R² > 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes (ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.