Modifications of black carbons and their influence on pyrene sorption

Sorption of pyrene on black carbons (BCs) obtained by heating sawdust at two temperatures (400 and 700 °C, denoted as 400BC and 700BC, respectively), as well as on modified BCs (via oxidation, oximation, and hydrolysis) was studied to investigate the role of BC structural characteristics in sorption of hydrophobic organic compounds. Pyrene was bound strongly by 700BC and 400BC, with organic carbon normalized distribution coefficients (K_oc) of 10^5.04-10^5.86 and 10^4.65-10^5.16, respectively, at equilibrium pyrene concentrations of 10-100 μg L⁻¹. Both chemical composition and pore distribution of the two BCs changed after modifications, which led to changes in their sorption characteristics for pyrene. After modifications, the linearity of pyrene sorption isotherm increased for 700BC but decreased for 400BC. For 700BC, both oxidation and oximation reduced pyrene sorption, with K_oc decreasing by 69.1-73.7% and 18.7-33.9%, respectively, whereas hydrolysis did not exert a significant influence. For 400BC, oxidation and hydrolysis reduced K_oc by 2.28-25.9% and 29.2-33.9%, respectively, while oximation increased K_oc. In most cases, the change in sorption capacity could be explained by the changes in C content and type, polarity, surface area, and micropore volume of the BCs; however, the role of conformation (the accessibility to sorption sites) could not be ignored.     

Comparison of manufactured and black carbon nanoparticle concentrations in aquatic sediments

In this paper, we show that concentrations of manufactured carbon-based nanoparticles (MCNPs) in aquatic sediments will be negligible compared to levels of black carbon nanoparticles (BCNPs). This is concluded from model calculations accounting for MCNP sedimentation fluxes, removal rates due to aggregation or degradation, and MCNP burial in deeper sediment layers. The resultant steady state MCNP levels are compared with BCNP levels calculated from soot levels in sediments and weight fractions of nanosized fractions of these soot particles. MCNP/BCNP ratios range from 10⁻⁷ to 10⁻⁴ (w:w). This suggests that the often acclaimed effect of MCNPs on organic pollutant binding and bioavailability will likely be below the level of detection if natural BCNPs are present, even if binding to MCNP is one to two orders of magnitude stronger than to BCNPs. Furthermore, exposure and toxic effects of MCNPs in sediments and soils will be negligible compared to that of BCNPs.     

Enhanced cytotoxicity of pentachlorophenol by perfluorooctane sulfonate or perfluorooctanoic acid in HepG2 cells

Chlorinated phenols and perfluoroalkyl acids (PFAAs) are two kinds of pollutants which are widely present in the environment. Considering liver is the primary toxic target organ for these two groups of chemicals, it is interesting to evaluate the possible joint effects of them on liver. In this work, the combined toxicity of pentachlorophenol (PCP) and perfluorooctane sulfonate (PFOS) or perfluorooctanoic acid (PFOA) were investigated using HepG2 cells. The results indicated that PFOS and PFOA could strengthen PCP’s hepatotoxicity. Further studies showed that rather than intensify the oxidative stress or promote the biotransformation of PCP, PFOS (or PFOA) might lead to strengthening of the oxidative phosphorylation uncoupling of PCP. By measuring the intracellular PCP concentration and the cell membrane properties, it was suggested that PFOS and PFOA could disrupt the plasma membrane and increase the membrane permeability. Thus, more cellular accessibility of PCP was induced when they were co-exposed to PCP and PFOS (or PFOA), leading to increased cytotoxicity. Further research is warranted to better understand the combined toxicity of PFAAs and other environmental pollutants.     

Historical record of black carbon in urban soils and its environmental implications

Energy use in urbanization has fundamentally changed the pattern and fluxes of carbon cycling, which has global and local environmental impacts. Here we have investigated organic carbon (OC) and black carbon (BC) in six soil profiles from two contrast zones in an ancient city (Nanjing) in China. BC in soils was widely variable, from 0.22 to 32.19 g kg⁻¹. Its average concentration in an ancient residential area (Zone 1) was, 0.91 g kg⁻¹, whereas in Zone 2, an industrial and commercial area, the figure was 8.62 g kg⁻¹. The ratio of BC/OC ranged from 0.06 to 1.29 in soil profiles, with an average of 0.29. The vertical distribution of BC in soil is suggested to reflect the history of BC formation from burning of biomass and/or fossil fuel. BC in the surface layer of soils was mainly from traffic emission (especially from diesel vehicles). In contrast, in cultural layers BC was formed from historical coal use. The contents of BC and the ratio of BC/OC may reflect different human activities and pollution sources in the contrasting urban zones. In addition, the significant correlation of heavy metals (Cu, Pb, and Zn) with BC contents in some culture layers suggests the sorption of the metals by BC or their coexistence resulted from the coal-involved smelting.     

道路环境黑碳变化特征及影响因素

为了分析道路环境黑碳浓度变化规律及影响因素,在北京APEC会议期间及前后对道路环境黑碳（BC）、NOx及PM2.5浓度进行测量,同时调查道路车流信息及气象数据,应用相关性分析、多元线性回归模型和排放强度计算等方法分析了机动车限行和气象条件对路边BC浓度的影响。结果显示：监测期间北土城东路路边的BC平均浓度为7.44 μg·m-3,限行期间10 d的平均浓度为4.43 μg·m-3,非限行期间21天的平均浓度为8.87 μg·m-3,机动车限行期间BC浓度下降50%。道路环境BC浓度高峰值分别出现在06：00-09：00和18：00-21：00,路边BC浓度与NOx和PM2.5浓度具有正线性相关性。限行期间总车流量下降52%,重型车辆流量变化不大,由于车流量下降和车速升高机动车尾气BC排放强度降低约15%。多元线性回归模型和情景分析结果显示限行期间气象条件和限行措施对BC浓度下降的贡献率分别为56%和30%,非限行期间如果采取限行措施可以使路边BC浓度下降34%。     

Quantification of activated carbon contents in soils and sediments using chemothermal and wet oxidation methods

Activated carbon (AC) strongly sorbs organic pollutants and can be used for remediation of soils and sediments. A method for AC quantification is essential to monitor AC (re)distribution. Since AC is black carbon (BC), two methods for BC quantification were tested for AC mixed in different soils and sediments: i) chemothermal oxidation (CTO) at a range of temperatures and ii) wet-chemical oxidation with a potassium dichromate/sulfuric acid solution. For three soils, the amount of AC was accurately determined by CTO at 375 °C. For two sediments, however, much of the AC disappeared during combustion at 375 °C, which could probably be explained by catalytic effects by sediment constituents. CTO at lower temperatures (325-350 °C) was a feasible alternative for one of the sediments. Wet oxidation effectively functioned for AC quantification in sediments, with almost complete AC recovery (81-92%) and low remaining amounts of native organic carbon (5-16%).     

Relationships between organic matter, black carbon and persistent organic pollutants in European background soils: Implications for sources and environmental fate

Black carbon (BC) and total organic carbon (TOC) contents of UK and Norwegian background soils were determined and their relationships with persistent organic pollutants (HCB, PAHs, PCBs, co-planar PCBs, PBDEs and PCDD/Fs) investigated by correlation and regression analyses, to assess their roles in influencing compound partitioning/retention in soils. The 52 soils used were high in TOC (range 54-460 mg/g (mean 256)), while BC only constituted 0.24-1.8% (0.88%) of the TOC. TOC was strongly correlated (p < 0.001) with HCB, PCBs, co-PCBs and PBDEs, but less so with PCDD/Fs (p < 0.05) and PAHs. TOC explained variability in soil content, as follows: HCB, 80%; PCBs, 44%; co-PCBs, 40%; PBDEs, 27%. BC also gave statistically significant correlations with PBDEs (p < 0.001), co-PCBs (p < 0.01) and PCBs, HCB, PCDD/F (p < 0.05); TOC and BC were correlated with each other (p < 0.01). Inferences are made about possible combustion-derived sources, atmospheric transport and air-surface exchange processes for these compounds.     

Kinetics of phenanthrene desorption from activated carbons to water

We determined the kinetics of phenanthrene desorption from three activated carbons to water using Tenax beads as an infinite sink for organic compounds in water. Desorption kinetic data very well fitted a biphasic kinetic model based on the presence of two different adsorption sites, viz. low-energy sites and high-energy sites. Rate constants for desorption to water from these two types of sites in the three activated carbons did not reveal a relation with activated carbon grain size. These rate constants were comparable to those for desorption of various organic compounds from hard carbon in various sediments.     

Size distribution of black (BC) and total carbon (TC) in Vienna and Ljubljana

During two campaigns in winter 2004, size segregated impactor samples (0.1-10 microm) and filter samples were taken in two Central European cities (Vienna, Austria and Ljubljana, Slovenia). The impactor samples were analyzed for major inorganic ions and short-chain organic acids, total carbon (TC) and black carbon (BC). Maximum concentrations of total mass were 71.6 microg m(-3) in Vienna and 73.1 microg m(-3) in Ljubljana. Minimum concentrations in Vienna were only half those in Ljubljana. The BC content of the aerosol was similar (ca. 8%), but the BC/TC ratio was higher in Vienna than in Ljubljana (0.39 vs. 0.29), reflecting the different contribution of diesel traffic emissions. The mass median diameters of the submicron size distributions of all major fractions (total mass, TC, BC and SO(4)(2-)) were smaller in Vienna (0.43 microm, 0.41 microm, 0.38 microm and 0.48 microm, respectively) than in Ljubljana (0.55 microm, 0.44 microm, 0.42 microm and 0.60 microm, respectively). Impactor/filter ratios for total mass were 0.79 in Vienna and 0.82 in Ljubljana, while the ratios for BC were 0.56 in Vienna and 0.49 in Ljubljana. An estimation of the mixing state of accumulation mode BC indicated that 33% and 37% of BC, respectively, are mixed externally to the aerosol in the accumulation size range in Vienna and Ljubljana.     

Release of polycyclic aromatic hydrocarbons from Yangtze River sediment cores during periods of simulated resuspension

The role of resuspension duration on release of 16 PAHs was measured experimentally using a particle entrainment simulator (PES). Three sediment cores were resuspended for 12h at 0.2 and 0.5N m(-2). PAHs in water column and total suspended solids (TSS) were monitored at intervals. After 0.25h of resuspension, PAH release was on average 42% of their concentrations after 12h of resuspension, indicating fast release of PAHs from sediments in an initial short time. Moreover, PAHs released faster at 0.5N m(-2) than at 0.2N m(-2); low molecular weight PAHs (2-3-ring) released faster than median molecular weight (4-ring) PAHs. PAH concentrations in TSS showed generally increase with time and differences in magnitudes based on sediment type and energy. Overall, the composition of sediments is the major factor in determining the amount of released PAHs, more so than the level of resuspension energy applied.     

水动力条件下重金属在沉积物上的吸附及其形态分布与转化

以北京近郊通州凉水河底泥沉积物为研究对象,利用环流槽(annular flume)模拟河流水力学条件,研究了重金属(Cr、Cu、Zn和Pb)在上覆水、悬浮颗粒物(SPMs)以及底泥中的交换、分配、形态分布与转化特征。结果表明,在动态水流环境条件下,加入到上覆水体中的重金属离子(5 mg/L)很快被吸附到SPMs上,模拟运行1 h后,上覆水中重金属的浓度(低流速条件下Zn除外),均不到初始值的3%;而SPMs中重金属的浓度在实验初期随着运行时间而降低,并且其浓度在低流速(0.2 m/s)时较高流速(0.35 m/s)条件下高,这是由于"颗粒物浓度效应"所致。在整个模拟运行周期(35 d)内,表层底泥中重金属形态发生了改变。其中,重金属的F4(硫化物+有机物)形态由于其与硫化物结合的形态被氧化而逐渐释放出来,并最终剩下不易氧化的有机物结合形态。与此同时,释放出的重金属通过再分配作用以易解析的F1～F3形态吸附于SPMs及底泥沉积物中,从而导致这3种形态浓度有所升高。     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Release flux of mercury from different environmental surfaces in Chongqing, China

An investigation was conducted to estimate mercury emission to the atmosphere from different environmental surfaces and to assess its contribution to the local mercury budget in Chongqing, China. Mercury flux was measured using dynamic flux chamber (DFC) at six soil sites of three different areas (mercury polluted area, farmland and woodland) and four water surfaces from August 2003 to April 2004. The mercury emission fluxes were 3.5 ± 1.2–8.4 ± 2.5 ng m⁻² h⁻¹ for three shaded forest sites, 85.8 ± 32.4 ng m⁻² h⁻¹ for farming field, 12.3 ± 9.8–733.8 ± 255 ng m⁻² h⁻¹ for grassland sites, and 5.9 ± 12.6–618.6 ± 339 ng m⁻² h⁻¹ for water surfaces. Mercury exchange fluxes were generally higher from air/water surfaces than from air/soil surfaces. The mercury negative fluxes were found in tow soil sites at overcast days (mean = −6.4 ± 1.5 ng m⁻² h⁻¹). The diurnal and seasonal variations of mercury flux were observed in all sites. The mercury emission responded positively to the solar radiation, but negatively to the relative humidity. The mercury flux from air/soil surfaces was significantly correlated with soil temperature, which was well described by an Arrhenius-type expression with activation energy of 31.1 kcal mol⁻¹. The annual mercury emission to the atmosphere from land surface is about 1.787 t of mercury in Chongqing.     

Polychlorinated naphthalenes (PCNs) in riverine and marine sediments of the Laizhou Bay area, North China

PCN congeners were analyzed in marine and riverine sediments of the Laizhou Bay area, North China. Concentrations of PCNs ranged from 0.12 to 5.1 ng g⁻¹ dry weight (dw) with a mean value of 1.1 ng g⁻¹ dw. The levels of PCNs varied largely, with industrial group approximately ten folds higher than those of the rural in riverine sediment. A strong impact by direct discharge from local factories was suggested. Similar compositional profiles were found within groups. High resemblance of compositional profiles between industrial samples and Halowax 1014 was observed. It was indicated that PCNs in riverine sediments were mainly from release of industrial usage, with additional contributions from industrial thermal process at certain sites. In marine sediments, it was suggested that PCNs along the coast of Laizhou Bay were mainly controlled by riverine input. While in the central bay, PCN distributions were possibly impacted by combined multiple factors.     

Testing the resistance of single- and multi-walled carbon nanotubes to chemothermal oxidation used to isolate soots from environmental samples

Quantification of natural and engineered carbon nanotubes (CNT) in the environment is urgently needed to study their occurrence and fate and to enable a proper risk assessment. Currently, such methods are lacking. Here, we tested the resistance of 15 structurally different CNTs to chemothermal oxidation at 375 °C (CTO-375), a method used to isolate soots from environmental samples. Depending on their structure, CNTs survived CTO-375 in proportions ranging from 26 to 93%. Standard addition of CNTs to soil and sediment yielded recoveries between 66 and 171%, demonstrating the capability of CTO-375 to isolate CNTs from complex environmental matrices. These data of pure and added CNTs correspond to recoveries obtained with “ordinary” soots under similar experimental conditions. Hence, soot fractions commonly isolated with CTO-375 from environmental matrices most probably encompass CNTs. Future work should attempt to enhance the method's selectivity, i.e., its capability to separate CNTs from other forms of soot.     

Testing the resistance of fullerenes to chemothermal oxidation used to isolate soots from environmental samples

We tested the resistance of five different fullerenes (C₆₀, C₇₀, C_76/78 mix, and C₈₄) to chemothermal oxidation at 375 °C (CTO-375), a method that has been used and tested for quantifying black carbon (BC) and CNTs in soils and sediments. C₆₀ survived CTO-375 the most (50%), while C₇₀ was the fullerene with the lowest survival rate (<1%). Standard additions of C₆₀ to soil and sediment reference materials yielded recoveries between 18 and 36%. Although lower than recoveries previously observed for soot and CNTs, these results demonstrate the capability of CTO-375 to partially isolate C₆₀ from solid environmental matrices. Standard additions of C₇₀, C_76/78, and C₈₄ yielded slightly higher survival rates when added to soil and sediment than in their pure form. These results indicate that the mineral matrices of these samples probably had a catalytic effect towards C₆₀ and a protective effect towards C₇₀, C_76/78, and C₈₄ during CTO-375.     

The spectroscopic studies of humic acid extracted from sediment collected at different seasons

Gocza?kowice Reservoir is the biggest water reservoir in the south of Poland. For our studies bottom sediments were collected from eight different places of the reservoir at various seasons of the year.EPR spectroscopy was applied to analyse both quantitatively and qualitatively the humic acids (HA) present in the samples. EPR spectra of the extracted HA exhibited broad lines from the paramagnetic metal ions and narrow lines from free radicals. The values of the free radical concentration obtained for HA amounted to 1.14-13.6 × 1016 spin g⁻¹ depending on the season and the place of sample collection. The values of the g factor obtained for HA were of the range 2.0027-2.0035.The EPR studies show that HA extracted from bottom sediment collected at various points of the Gocza?kowice Reservoir exhibit similar physical-chemical properties. It was also observed that the depth of the reservoir affects the content of the oxygen functional groups as well as the free radical concentration in HA.The identification of the functional groups was done by means of IR. UV/VIS spectroscopy was used to estimate the maturity of the HA.     

Heavy metal contamination in surface sediments of Yangtze River intertidal zone: An assessment from different indexes

Surface sediments (0-5 cm) from 59 stations within the Yangtze River intertidal zone (YRIZ) were sampled for metal contamination analysis in April and August 2005. The concentrations ranged (in mg kg⁻¹ dry weight): Al, 40,803-97,213; Fe, 20,538-49,627; Cd, 0.12-0.75; Cr, 36.9-173; Cu, 6.87-49.7; Mn, 413-1,112; Ni, 17.6-48.0; Pb, 18.3-44.1; and Zn, 47.6-154; respectively. Among the 59 sampling stations, enrichment factors (EF) indicate enrichment of Cd (52 stations), Cr (54 stations), Cu (5 stations), Ni (26 stations), Pb (5 stations) and Zn (5 stations). Geoaccumulation indexes (I_geo) also suggest individual metal contamination in localized areas. This study indicates that Cd, Cr and Ni enrichment in the YRIZ sediment is widespread whereas Cu, Mn, Pb and Zn enrichment is localized or nonexistent. Factor and cluster analyses indicate that Cd is associated with total organic carbon whereas Cu, Cr, Ni, Pb and Zn have a close association with Mn.     

Contrasting effects of black carbon amendments on PAH bioaccumulation by Chironomus plumosus larvae in two distinct sediments: role of water absorption and particle ingestion

Two sediment matrices with different characteristics were amended with chars from different sources for bioaccumulation assay with filter-feeding Chironomus plumosus larvae. Chars greatly decreased porewater concentrations of PAHs (C_iw) measured using polyethylene devices in sediments. In organic rich sediment matrix-based systems where suspended char particles were absent, PAH concentrations in larvae (C_iB) were significantly correlated with C_iw, and there was no difference in water-based bioaccumulation factors (BAFs) between different treatments, suggesting that water absorption was the main contaminant uptake route for larvae. In organic poor sediment matrix-based systems where suspended char particles were present, poor Pearson correlation between C_iB and C_iw was found, but there was a significant linear increase of BAF values with char contents, which indicated that ingestion of suspended char particles could also be important for PAH bioaccumulation. Therefore, we need to rethink of the effectiveness and risks for the application of black carbon to sediment/soil remediation.     

2种启动方式下CSTR厌氧甲烷发酵系统的运行特性比较

厌氧产甲烷菌生长缓慢,对生境环境尤为敏感,其富集难且慢,所以厌氧反应器的快速启动一直是热点研究问题。为摸清连续流搅拌槽式反应器（CSTR）处理糖蜜废水的适宜启动条件和调控方法,比较了两种启动方式下CSTR厌氧甲烷发酵系统的运行特性。结果显示,以啤酒废水污水处理车间的剩余污泥为种泥,在HRT为18 h、温度35℃条件下,进水COD为4 000 mg·L-1时直接启动CSTR厌氧反应器,系统因挥发酸积累,产甲烷菌群活性受限,难以富集培养,经过近103 d的运行,系统未形成高效的厌氧甲烷发酵微生物菌群结构体系;而当采用保持HRT18 h不变,进水COD阶段性提升至4 000 mg·L-1的启动方式时,产甲烷菌群活性较高,能在较短时间内得到有效富集和培养,CSTR能成功培养具有完整甲烷发酵功能的微生物菌,COD去除率可在65 d内达到56%,反应器成功启动。