GIS-based source identification and apportionment of diffuse water pollution: perfluorinated compound pollution in the Tokyo Bay basin

To efficiently reduce perfluorinated compound (PFC) pollution, it is important to have an understanding of PFC sources and their contribution to the pollution. In this study, source identification of diffuse water pollution by PFCs was conducted using a GIS-based approach. Major components of the source identification were collection of the monitoring data and preparation of the corresponding geographic information that was extracted from a constructed GIS database. The spatially distributed pollution factors were then explored by multiple linear regression analysis, after which they were visually expressed using GIS. Among the 35 PFC homologues measured in a survey of the Tokyo Bay basin, 18 homologues were analyzed. Pollution by perfluorooctane sulfonate (PFOS) was explained well by the percentage of arterial traffic area in the basin, and the 84% variance of the measured PFOS concentration was explained by two geographic variables, arterial traffic area and population. Source apportionment between point and nonpoint sources was conducted based on the results of the analysis. The contribution of PFOS from nonpoint sources was comparable to that from point sources in several major rivers flowing into Tokyo Bay. Source identification and apportionment using the GIS-based approach was shown to be effective, especially for ubiquitous types of pollution, such as PFC pollution.     

Time trends of perfluorinated compounds from the sediment core of Tokyo Bay, Japan (1950s-2004)

Perfluorinated compounds (PFCs) were detected in sediment core samples collected in Tokyo Bay to reveal their time trends. The core sample deposited during 1950s-2004 was divided into two- to three-year intervals and the concentrations of 24 types of PFCs were determined. Perfluorooctane sulfonate (PFOS) decreased gradually from the early 1990s and its precursor decreased rapidly in the late 1990s, whereas perfluorooctanoic acid (PFOA) increased rapidly. The observed trends were regarded as a reflection of the shift from perfluorooctyl sulfonyl fluoride (PFOSF)-based products to telomer-based products after the phaseout of PFOSF-based products in 2001. The branched isomers of perfluoroundecanoic acid (PFUnDA) and perfluorotridecanoic acid (PFTrDA) were detected in the sample with its ratio of linear-isomer/branched-isomer concentrations decreasing. In this study, we revealed that the sediment core can serve as a tool for reconstructing the past pollution trend of PFCs and can provide interesting evidence concerning their environmental dynamics and time trend.     

Spatial distribution and vertical profile of polybrominated diphenyl ethers and hexabromocyclododecanes in sediment core from Tokyo Bay, Japan

Brominated flame retardants (BFRs), hexabromocyclododecanes (HBCDs) and polybrominated diethyl ethers (PBDEs) were detected in three sediment cores and six surface sediments of Tokyo Bay, Japan. HBCDs were detected for the first time in this region with concentrations ranging from 0.056 to 2.3 ng/g dry wt, implying their widespread contamination, even though their concentrations were lower than summation operatorPBDEs (di- to nona-BDEs) and BDE-209. Levels of these compounds were higher near to the highly populated industrial area of the bay implicating industrial and human activities as sources of these compounds. Summation operatorPBDEs increased in the sediment layer up to the mid-1990s and decreased afterwards, whereas BDE-209 showed an increasing trend until now, following the usage of different commercial BDE mixtures. HBCDs first appeared in the mid-1970s and increased until today. The annual surficial flux of HBCDs (0.62-2.4 ng/cm2/yr) is equal to summation operatorPBDEs (0.95-2.6 ng/cm2/yr) but lower than that of BDE-209 (17-58 ng/cm2/yr).     

Horizontal distribution of steroid estrogens in surface sediments in Tokyo Bay

A monitoring survey was conducted to investigate the distribution of steroid estrogens and their conjugates in surface sediments of Tokyo Bay for the first time, which is known as one of the most heavily polluted marine embayments in the world. The surface sediment samples were collected at 20 locations covering the whole area of Tokyo Bay and analyzed for steroid estrogens and their conjugates using liquid chromatography-tandem mass spectrometry. The concentrations of 17beta-estradiol (beta-E2) and estrone (E1) ranged from ND (below the detection limit; <0.07) to 0.59 and from 0.05 to 3.60 ng g-1 dry, respectively. Those concentrations were higher in the northern part of the bay, which is directly receiving huge quantities of pollutants from adjacent rivers containing a large amount of municipal and industrial wastewater. 17alpha-Estradiol (alpha-E2) and estrone-3-sulfate (E1-3S) were detected in some of the samples, whereas neither of the other conjugates, estriol (E3) or 17alpha-ethynylestradiol (EE2), was found.     

Existence of nonpoint source of perfluorinated compounds and their loads in the Tsurumi River basin, Japan

Products containing perfluorinated compounds (PFCs) have been widely used during the last 50 years. As a result, worldwide environmental pollution by PFCs has been reported. The sources of PFC pollution in the aquatic environment have been poorly understood. In this study, river water and sewage treatment plant (STP) effluent were sampled along the stretch of the Tsurumi River and also at a fixed station in the river. The concentrations of perfluorooctanesulfonate (PFOS), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were measured. With an increase in river flow rate, it was observed that the PFC concentrations in the river water at fixed station were remained the same or increased for PFOS (179.9+/-34.4-179.6+/-69.5 ng l(-1)), PFHxA (5.5+/-0.8-9.0+/-2.6 ng l(-1)), PFHpA (3.1+/-0.3-4.4+/-1.0 ng l(-1)), and PFOA (15.9+/-0.3-13.4+/-2.5 ng l(-1)) whereas the concentration of PFNA (38.0+/-3.3-15.4+/-3.0 ng l(-1)) and PFDA (3.9+/-0.3-2.1+/-0.3 ng l(-1)) were decreased. On the other hand, the loads of every PFC increased with an increase in river flow rate. The loads of PFCs in rain runoff were estimated to be 2-11 times greater than those in STP effluents that are discharged into the river. These results indicate the existence of a PFC nonpoint source (NPS) and its impact to the total PFC load of river is significant.     

Source and behavior analyses of dioxins based on congener-specific information and their application to Tokyo Bay basin

Identification of pollution sources and estimation of their contribution to dioxin pollution are important for taking better countermeasures against such sources. The information based on seventeen 2,3,7,8-chlorine-substituted congeners and 10 homologues is usually not sufficient for source identification. The usefulness of detailed congener-specific information of tetra- to octachlorinated polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans was examined by principal component analysis and compared with conventional dioxin information. It was revealed that congener-specific information was far more effective for source identification than conventional information. For source apportioning, it was shown that multiple regression analysis with detailed source congener profiles could be carried out successfully when calculations were performed for individual homologues. This was because of the large variation in homologue composition in source dioxin profiles in addition to the difference in environmental behavior among the homologues.The newly proposed methods for statistical analysis were applied to the estimation of dioxin mass balance in Tokyo Bay basin. It was found that Tokyo Bay sediment core contained dioxins from three major sources: combustion, pentachlorophenol (PCP), and chloronitrophen (CNP). PCP and CNP contained large amounts of dioxin as impurity and were used extensively as paddy field herbicides in Japan in the past. The total dioxin load from the two herbicides to the basin during the past 45 years (1951-1995) was estimated to be five times larger than that from combustion source in terms of toxic equivalents (WHO-TEQ). However, in the surface sediment of the bay, the contribution from the herbicides was nearly equal to that from combustion. The herbicide contribution peaked during the 1960s and 1970s and gradually decreased thereafter.     

Spatial distribution of pollution in an urban stormwater infiltration basin

Infiltration basins are frequently used for stormwater drainage. Because stormwater is polluted in highly toxic compounds, assessment of pollution retention by infiltration basins is necessary. Indeed, if basins are not effective in trapping pollution, deep soil and groundwater may be contaminated. This study's objective is to investigate soil pollution in infiltration basins: spatial distribution of soil pollution, optimisation of the number of soil samples and a contamination indicator are presented. It is part of a global project on long-term impact of stormwater infiltration on groundwater. Soil sampling was done on a basin in suburban Lyon (France). Samples were collected at different depths and analysed for nutrients, heavy metals, hydrocarbons and grain size. Pollutant concentrations decrease rapidly with depth while pH, mineralisation and grain size increase. Sustainable metal concentrations are reached at a 30-cm depth, even after 14 years of operation; hydrocarbon pollution is deeper. Principal component analysis shows how pollutants affect each level. The topsoil is different from other levels. Three specifically located points are enough to estimate the mass of pollution trapped by the basin with a 26% error. The proposed contamination indicator is calculated using either average level concentrations or maximum level concentrations. In both cases, the topsoil layer appears polluted but evaluation of lower levels is dependent on the choice of input concentrations.     

Distribution and desorption of perfluorinated compounds in fractionated sediments

This study provides particle-scale understanding of perfluorinated compounds (PFCs) distribution in sediments collected from two locations in Tianjin, China. The sediments were fractionated according to particle size and density. Even though lower density carbonaceous fractions contributed only 17.8-22.3% of the total sediment mass, they displayed stronger affinity to PFCs with much higher PFC concentrations than in the heavy fractions. Hydrophobic interaction predominated the partition of longer chain PFCs while electrostatic interaction could affect the sorption of short chain PFCs in sediment fractions. The individual PFC concentrations increased with increasing perfluorocarbon chain length, and the concentrations of perfluoroalkanesulfonates (PFSAs) in the same sediment fraction were higher than perfluorocarboxylates (PFCAs) with the same chain length. Log K(oc) was in the range of 1.70-3.80 for C5-C12 PFCAs and 1.75-2.97 for C4-C8 PFSAs. Desorption experiments indicated desorption became difficult as the chain length increased, and PFSAs were harder to be desorbed than the corresponding PFCAs.     

Spatial distribution of pesticides,organochlorine compounds,PBDEs, and metals in surface marine sediments from Cartagena Bay,Colombia

Environmental Science and Pollution Research - Cartagena Bay is an estuarine system located in the Caribbean Sea (Colombia, South America), that receives fresh water from Canal del Dique, which is...     

Effect of dissolved organic carbon on the environmental distribution of nonpolar organic compounds

The effect of dissolved organic carbon on the process of pollutant sorption to aquatic sediments was studied using sediments from the Boonton Reservoir/Rockaway River system in northern New Jersey. Addition of DOC to the aqueous phase reduced the sorption of DDT to sediments, but had no effect on the sorption of Lindane. The effect of the DOC is to increase the amount of DDT in the soluble phase and enable transport of the compound throughout an aquatic system. The apparent influence of DOC on the equilibrium distribution of organic compounds is illustrated by modifying an existing environmental model.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Wet deposition of poly- and perfluorinated compounds in Northern Germany

Twenty precipitation samples were taken concurrently with air samples at a northern German monitoring site over a period of 7 months in 2007 and 2008. Thirty four poly- and perfluorinated compounds (PFC) were determined in rain water samples by solid phase extraction and HPLC-MS/MS analysis. Seventeen compounds were detected in rain water with ΣPFC concentrations ranging from 1.6 ng L⁻¹ to 48.6 ng L⁻¹. Perfluorooctanoate (PFOA) and perfluorobutanate (PFBA) were the compounds that were usually observed in highest concentrations. Calculated ΣPFC deposition rates were between 2 and 91 ng m⁻² d⁻¹. These findings indicate that particle phase PFC are deposited from the atmosphere by precipitation. A relationship between PFC wet deposition and air concentration may be established via precipitation amounts. Trajectory analysis revealed that PFC concentration and deposition estimates in precipitation can only be explained if a detailed air mass history is considered.     

Behavior of perfluorinated compounds in soils during leaching experiments

Perfluorinated compounds (PFCs) can be detected worldwide in both, soil and water. In order to study the leaching behavior of this heterogeneous group of compounds in soil, flow-through column experiments have been conducted. Ten perfluoro carboxylates and four perfluoro sulfonates ranging from C4 to C14 in chain length, and contaminated sewage sludge, have been used to spike a standard soil. The aqueous column effluent was analyzed using liquid chromatography tandem mass spectrometry (LC-MS/MS) with direct injection. The observed percolation velocity seems to be strongly correlated with the length of the perfluorinated chain. Other factors that additionally contribute to the leaching behavior are the functional group of the PFC, the organic carbon content of the soil and the presence of other adsorbates. A mass balance calculation showed that perfluorobutanoic acid can adsorb strongly to the soil, when no PFC with longer carbon chain are present. Only about 60% of the added perfluorobutanoic acid could be detected in the percolate water. The missing amount started to elute again when longer chain PFC or stearate were added to the soil. Thus it would appear that larger and more lipophilic molecules can displace shorter PFC from their binding sites in the soil.The results of a monitoring study using 32 surface water samples and 150 groundwater samples confirm that the PFC with the highest concentrations in groundwater are the short chain PFC with less than 7 (fluorinated) carbon atoms. The dominating PFC in surface waters are perfluorooctanoic acid and perfluorooctane sulfonic acid.     

稻田土壤溶液中溶解性有机氮、碳的空间分布及其微生物降解特性

通过测坑定位试验,测定了稻田不同深度土壤溶液中溶解性有机氮(DON)、溶解性有机碳(DOC)的含量,并将原位提取的土壤溶液加入到人工土壤中,开展土壤溶液中DON、DOC的微生物降解试验,研究不同施肥处理DON、DOC的含量分布及其微生物降解特性。结果表明:(1)两种施肥处理0~10cm土壤溶液中TN、DON显著低于其他两层土壤;土壤溶液中DON占TN的比例均在62.9%~79.8%,为氮素组成的主要形式。(2)有机无机混合肥处理中DOC占TC的比例随土壤深度加大而逐渐增加,比例为21.1%~25.1%,而无机肥处理中DOC占TC比例则是逐渐下降,比例为18.9%~20.0%。(3)稻田土壤溶液中DON和DOC具有较好的微生物降解特性。降解28d后,DON占初始DON的30.1%~34.9%,而DOC占初始DOC的24.3%~28.2%。     

城市污水处理厂中全氟化合物的存在及去除效果研究

建立了一种基于超高效液相色谱/串联质谱的方法,实现了对北京3个污水处理厂污水中12种全氟化合物(PFCs)的快速、灵敏地定量分析.结果表明,城市污水处理厂进水和出水中短链的全氟丁酸(PFBA)、全氟戊酸(PFPA)和全氟丁磺酸(PFBS)是主要污染物,其中出水中PFBs的质量浓度高达253 ng/L.污水生物处理后,出...     

Determinants of maternal and fetal exposure and temporal trends of perfluorinated compounds

In recent years, some perfluorinated compounds (PFCs) have been identified as potentially hazardous substances which are harmful to the environment and human health. According to limited data, PFC levels in humans could be influenced by several determinants. However, the findings are inconsistent. In the present study, perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were measured in paired maternal and cord serum samples (N?=?237) collected between 1978 and 2001 in Southern Sweden to study the relationship between these and to investigate several potential determinants of maternal and fetal exposure to PFCs. Time trends of PFCs in Swedish women were also evaluated. The study is a part of the Fetal Environment and Neurodevelopment Disorders in Epidemiological Research project. PFOS, PFOA, and PFNA levels (median) were higher in maternal serum (15, 2.1, and 0.24 ng/ml, respectively) than in cord serum (6.5, 1.7, and 0.20 ng/ml, respectively). PFC levels were among the highest in women originating from the Nordic countries and the lowest in women from the Middle East, North Africa, and sub-Saharan Africa. Multiparous women had lower serum PFOA levels (1.7 ng/ml) than primiparous women (2.4 ng/ml). Maternal age, body mass index, cotinine levels, and whether women carried male or female fetuses did not affect serum PFC concentrations. Umbilical cord serum PFC concentrations showed roughly similar patterns as the maternal except for the gestational age where PFC levels increased with advancing gestational age. PFOS levels increased during the study period in native Swedish women. In summary, PFOS levels tend to increase while PFOA and PFNA levels were unchanged between 1978 and 2001 in our study population. Our results demonstrate that maternal country of origin, parity, and gestational age might be associated with PFC exposure.     

Spatial distribution and ecotoxicological risk assessment of heavy metals in surface sediments of the southern Bohai Bay, China

The concentrations of heavy metals (Cd, Cr, Cu, Ni, Pb, and Zn) and organic carbon in surface sediments, collected from the southern Bohai Bay, were determined to assess the potential contamination and determine the environmental risks associated with heavy metals. Results showed that heavy metal concentrations in the sediments generally met the China Marine Sediment Quality criteria. Both the ecotoxicological index and the potential ecological risk index suggest that the combined ecological risk of the six studied metals may be low, with the highest ecotoxicological potential zones located in the offshore area. The methods of enrichment factor and geoaccumulation index suggested that elevated concentrations of Cd, Cr, and Ni are presented in the region. Multivariate analysis also indicated that the lithogenic factor dominates the distribution of most part of the considered metals in the study area, whereas Cd and Cr are clearly influenced by anthropogenic inputs. The results of this study are likely to be a useful tool to authorities in charge of sustainable marine management.     

First assessment of population exposure to perfluorinated compounds in Flanders, Belgium

With the objective to evaluate exposure of the population in Flanders (Belgium) to perfluorinated compounds (PFCs), we measured perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in settled dust in homes and offices, in a selection of food items from local origin, in drinking-water and in human serum. We complemented the data with results from a literature survey. Based on this dataset we calculated intake by children and adults from food, drinking-water, settled dust and soil, and air. Dietary exposure dominated overall intake. For adults, average dietary intake equalled 24.2 (P95 40.9) ng PFOS kg⁻¹ d⁻¹ and 6.1 (P95 9.6) ng PFOA kg⁻¹ d⁻¹, whereas for children the dietary intake was about 3 times higher. Predicted intake is high when compared to assessments in other countries, and to serum levels from Flanders, but comparable to the intakes published by The European Food Safety Authority (EFSA) in 2008. Intake of PFOS and PFOA remained below the Tolerable Daily Intake.