Occurrence of perfluorinated organic acids in the North and Baltic Seas. Part 2: distribution in sediments

Purpose  

The distribution of polar perfluorinated compounds (PFCs) in sea water of the North and Baltic Seas has been described in part 1 of this study. In part 2, their occurrence in sediments is described in order to further investigate their distribution routes and possible sinks.     

Occurrence of perfluorinated carboxylic acids (PFCAs) in personal care products and compounding agents

Perfluorinated carboxylic acids (PFCAs), including perfluorooctanoic acid (PFOA), are persistent organic pollutants that pose human health risks. However, sources of contamination and exposure pathways of PFCAs have not been explored. In this study, PFCA concentrations were quantified in personal care products. Among 24 samples that listed fluorinated compounds, such as polyfluoroalkyl phosphate esters (PAPs), in their international nomenclature of cosmetic ingredients (INCI) labels, 21contained PFCAs (13 of 15 cosmetic samples, and 8 of 9 sunscreen samples). The concentrations of total PFCAs ranged from not detected to 5.9 μg g⁻¹ for cosmetics and from not detected to 19 μg g⁻¹ for sunscreens. We also investigated components of PFCAs in cosmetics and sunscreens. Commercially available compounding agents, mica and talc, which were treated with PAPs were analyzed and high concentrations of PFCAs were detected (total PFCAs 2.5 μg g⁻¹ for talc treated with PAPs, 35.0 μg g⁻¹ for mica treated with PAPs). To the best of our knowledge, this is the first report on contamination of end consumer products containing PAPs with high concentrations of PFCAs.     

Passive sampling of perfluorinated acids and sulfonates using polar organic chemical integrative samplers

The applicability of a polar organic chemical integrative sampler (POCIS) for detection and determination of perfluorinated acids and sulfonates in water was studied under field conditions. Standard POCIS configurations (i.e., pharmaceutical and pesticide) were deployed in effluent from a wastewater treatment plant for 1, 2, and 3 weeks. Ten of 15 target compounds were found in POCIS, five of which were quantified in wastewater. Pest-POCIS appeared more effective for the sampling, while Pharm-POCIS had a more rapid uptake kinetic, which leads to faster saturation or equilibrium. The results showed that the pesticide configuration is probably more suitable for the sampling of this class of compounds. Based on average concentration in water over the sampling period and amount of compound adsorbed in the POCIS, we calculated sampling rates for five studied compounds and obtained values of 0.034 to 0.222 L?day^?1.     

Occurrence and distribution of atmospheric organic micropollutants in conifer needles

The distribution of some chlorinated hydrocarbons(p,p′-DDT, p,p′-DDE,α-HCH,γ-HCH,HCB) in spruce (Picea abies) needles was investigated. A comparision of concentrations in the wax with that of the remaining needle and time-resolved washing of the needle-surface shows the distribution behaviour of these substances.     

Concentrations of PFOS, PFOA and other perfluorinated alkyl acids in Australian drinking water

Perfluorinated alkyl acids (PFAAs) are persistent environmental pollutants, found in the serum of human populations internationally. Due to concerns regarding their bioaccumulation, and possible health effects, an understanding of routes of human exposure is necessary. PFAAs are recalcitrant in many water treatment processes, making drinking water a potential source of human exposure. This study was conducted with the aim of assessing the exposure to PFAAs via potable water in Australia. Sixty-two samples of potable water, collected from 34 locations across Australia, including capital cities and regional centers. The samples were extracted by solid phase extraction and analyzed via liquid chromatography/tandem mass spectrometry for a range of perfluoroalkyl carboxylates and sulfonates. PFOS and PFOA were the most commonly detected PFAAs, quantifiable in 49% and 44% of all samples respectively. The maximum concentration in any sample was seen for PFOS with a concentration of 16 ng L⁻¹, second highest maximums were for PFHxS and PFOA at 13 and 9.7 ng L⁻¹. The contribution of drinking water to daily PFOS and PFOA intakes in Australia was estimated. Assuming a daily intake of 1.4 and 0.8 ng kg⁻¹ bw for PFOS and PFOA the average contribution from drinking water was 2-3% with a maximum of 22% and 24% respectively.     

Occurrence and distribution of triclosan in the German Bight (North Sea)

The potential of triclosan (TCS) acting as an endocrine disruptor has led to growing concern about the presence of TCS in the environment. In this study, seawater samples were collected from the German Bight during sampling campaigns conducted with the German research ships Gauss and Ludwig Prandtl. TCS was determined both in the dissolved phase and in the suspended particulate matters with concentrations ranging 0.8-6870 pg L⁻¹ and <1-95 pg L⁻¹, respectively. High concentrations of TCS were present in the estuaries of the Elbe and the Weser, indicating significant input of TCS by the river discharge. The correlation coefficient (R²) between the dissolved concentration and salinity was 0.79 for the data obtained from the Gauss cruise, showing an obvious declining trend from the coast to the open sea.     

Occurrence and partition of perfluorinated compounds in water and sediment from Liao River and Taihu Lake, China

The concentrations of four perfluorinated sulfonate acids (PFSAs) and 10 perfluorinated carboxylate acids (PFCAs) were measured in water and sediment samples from Liao River and Taihu Lake, China. In the water samples from Taihu Lake, PFOA and PFOS were the most detected perfluorinated compounds (PFCs); in Liao River, PFHxS was the predominant PFC followed by PFOA, while PFOS was only detected in two of the samples. This suggests that different PFC products are used in the two regions. PFOS and PFOA in both watersheds are at similar level as in the rivers of Japan, but significantly lower than in Great Lakes. The contributions of PFOS and long chain PFCAs in sediments were much higher than in water samples of both watersheds, indicating preferential partition of these PFCs in sediment. The concentrations of PFOS and PFOA were three orders of magnitude of lower than that of polycyclic aromatic hydrocarbons in the same sediments. The average sediment-water partition coefficients (log K_oc) of PFHxS, PFOS and PFOA were determined to be 2.16, 2.88 and 2.28 respectively.     

Survey of perfluorinated alkyl acids in Finnish effluents, storm water, landfill leachate and sludge

The objective of the Control of Hazardous Substances in the Baltic Sea (COHIBA) project is to support the implementation of the HELCOM Baltic Sea Action Plan regarding hazardous substances by developing joint actions to achieve the goal of “a Baltic Sea with life undisturbed by hazardous substances”. One aim in the project was to identify the most important sources of 11 hazardous substances of special concern in the Baltic Sea. Among them are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In this study, four perfluorinated alkyl acids (PFAAs) were studied: PFOA, PFOS, perfluorohexanoic acid (PFHxA) and perfluorodecanoic acid (PFDA). The occurrence of PFAAs in municipal and industrial wastewater treatment plant effluents (MWWTP1-3, IWWTP1), target industry effluent, storm water, landfill leachate and sludge was studied. Effluents were analysed six times and storm water, leachate and sludge were analysed twice, once in the warm season and once in the cold, during a 1-year sampling campaign. PFOS prevailed in two municipal effluents (MWWTP1 and 3) and industrial effluent (IWWTP1; 7.8–14, 8.0–640 and 320–1,300 ng/l, respectively). However, in one municipal effluent (MWWTP2) PFOA was, in a majority of sampling occasions, the predominant PFAA (9–15 ng/l) followed by PFOS (3.8–20 ng/l). The highest PFAA loads of the municipal effluents were found in the MWWTP3 receiving the biggest portion of industrial wastewater. In storm water the highest concentration was found for PFHxA (17 ng/l). The highest concentration of PFOS and PFOA were 9.9 and 5.1 ng/l, respectively. PFOS, PFOA and PFHxA were detected in every effluent, storm water and landfill leachate sample, whereas PFDA was detected in most of the samples (77 %). In the target industry, PFOS concentrations varied between 1,400 and 18,000 μg/l. In addition, on one sampling occasion PFOA and PFHxA were found (0.027 and 0.009 μg/l, respectively). For effluents, PFAA mass flows into the Baltic Sea were calculated. For municipal wastewater treatment plants average mass flows per day varied for PFOS between 1,073 and 38,880 mg/day, for PFOA 960 and 2,700 mg/day, for PFHxA 408 and 1,269 mg/day and for PFDA 84 and 270 mg/day. In IWWTP mass flows for PFOS, PFOA, PFHxA and PFDA were 495 mg/d, 28 mg/d, 23 mg/d and 0.6 mg/g, respectively.     

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...     

The changing state of contamination in the Lagoon of Venice. Part 1: organic pollutants

The Lagoon of Venice is a transitional environment suffering from industrial, urban and agricultural impact. Recently the mechanical clam fishing, preventing a regular deposition of sediments has made sampling of cores suitable for radiodating very problematic. Therefore, in this study, in order to assess temporal and spatial trends of contamination, the same sampling scheme was repeated three times over a 12-year period. The concentrations of PCBs, PAHs and organochlorine pesticides were measured in the uppermost 5 cm of sediments collected in 25 sites in the central portion of the lagoon during three campaigns conducted in 1987, 1993 and 1998. Analytical results, validated statistically, indicated that, while PCB and pesticide concentrations tend to decrease during the considered period of time, PAH do not, showing that the input rate of these compounds to the lagoon environment is still important. A spatial trend of pollution was also found in the lagoon for PCBs and pesticides, which decrease from the sources, namely the industrial zone and the mouths of rivers, to areas closer to the sea: a reduction up to 80% and 90%, respectively, was monitored. PAH contamination, originating chiefly from incomplete combustion of fossil fuels, as inferred from ratios of congeners, was mainly located around the historical center of Venice, where most of the boat traffic is concentrated and has an increasing trend.     

Kinetics of peat soil dissolved organic carbon release from bed sediment to water. Part 1. Laboratory simulation

Temporary water reservoirs built upon peat soil may exhibit water quality impairment from elevated dissolved organic carbon (DOC). Microbiological decay of the organic carbon in the bed with subsequent release produces "tea" colored water which may require treatment prior to use. This paper describes laboratory experiments designed to obtain data on the release process of DOC from soils containing 0.65%, 10% and 19% carbon. Parallel experiments with and without sodium azide treatment clearly distinguished the initial release of a porewater residual fraction and the microbial produced fraction. A one to two day quick-release DOC fraction, which ranges from 28% to 50%, first emerged from the bed, Step-1. This was followed by a constant rate of DOC production over four weeks, Step-2. The Step-2 average production rates were 3.4, 12, and 31 mg DOC/kg(dry)/day for the respective soils and increased as soil carbon content increased. The inorganic carbon (IC) behaved oppositely; its rate of production decreased with increasing soil carbon. A consistent and simple rate equation described the Step-2 DOC production process. This and other evidence obtained provided the basis for developing a mathematical model that couples both steps of the bed-to-water DOC release chemodynamics. The model is presented in a companion paper (Part-2).     

Occurrence and change of estrogenic activity in the process of drinking water treatment and distribution

From 2010 to 2012, the Yangtze River and Hanjiang River (Wuhan section) were monitored for estrogenic activities during various water level periods. Using a recombinant yeast estrogen screen (YES) assay, 54 water samples were evaluated over the course of nine sampling campaigns. The mean 17β-estradiol equivalent (EEQ) value of raw water from the Yangtze River was 0–5.20 ng/L; and the EEQ level from the Hanjiang River was 0–3.22 ng/L. In Wuhan, drinking water treatment plants (DWTPs) using conventional treatments reduced estrogenic activities by more than 89 %. In general, water samples collected during the level period showed weaker estrogenic activities compared to those collected during the dry period. The samples collected in 2010 showed the strongest estrogenic activities of the 3-year period. The lack of correlations between estrogenic activities and selected common water quality parameters showed that estrogenic activity cannot be tied to common water quality parameters.     

Distribution and diagenesis of organic and inorganic phosphorus in sediments of the Baltic proper.

Measurements of the distribution of organic and inorganic phosphorus in the sediment have been performed at 10 sites, in the central-northern Baltic proper. Variations in deposition environment and environmental properties, such as redox chemistry and bottom water dynamics, apparently affect the distribution by altering the supply and diagenesis of organic and inorganic phosphorus constituents. The C/P and the N/P ratios of the sediment are highly divergent (higher) from the average Redfield ratio for marine living organisms at all examined sites. This indicates preferential autolytic organic phosphorus degradation and/or (deeper down in the sediment) altered input of terrestrial organic matter. The redox condition seems to affect the degradation efficiency of the organic matter since higher concentrations of C(org) occur at anoxic conditions than at oxic. At two sites significant amounts of C(inorg) have been detected indicating authigenic precipitation of carbonates. Further, authigenic precipitation of phosphate minerals also seems to occur at certain environmental conditions.     

Occurrence and distribution of organic trace substances in waters from the Three Gorges Reservoir, China

This study deals with the evaluation of water quality of the Three Gorges Reservoir (TGR) in order to assess its suitability as a raw water source for drinking water production. Therefore, water samples from (1) surface water, (2) tap water, and (3) wastewater treatment plant effluents were taken randomly by 2011–2012 in the area of the TGR and were analyzed for seven different organic contaminant groups (207 substances in total), applying nine different analytical methods. In the three sampled water sources, typical contaminant patterns were found, i.e., pesticides and polycyclic aromatic hydrocarbons (PAH) in surface water with concentrations of 0.020–3.5 μg/L and 0.004–0.12 μg/L, disinfection by-products in tap water with concentrations of 0.050–79 μg/L, and pharmaceuticals in wastewater treatment plant effluents with concentrations of 0.020–0.76 μg/L, respectively. The most frequently detected organic compounds in surface water (45 positives out of 57 samples) were the pyridine pesticides clopyralid and picloram. The concentrations might indicate that they are used on a regular basis and in conjunction in the area of the TGR. Three- and four-ring PAH were ubiquitously distributed, while the poorly soluble five- and six-ring members, perfluorinated compounds, polychlorinated biphenyls, and polybrominated diphenyl ethers, were below the detection limit. In general, the detected concentrations in TGR are in the same range or even lower compared to surface waters in western industrialized countries, although contaminant loads can still be high due to a high discharge. With the exception of the two pesticides, clopyralid and picloram, concentrations of the investigated organic pollutants in TGR meet the limits of the Chinese Standards for Drinking Water Quality GB 5749 (Ministry of Health of China and Standardization Administration of China 2006) and the European Union (EU) Council Directive 98/83/EC on the quality of water intended for human consumption (The Council of the European Union 1998), or rather, the EU Directive on environmental quality standards in the field of water policy (The European Parliament and The Council of the European Union 2008). Therefore, the suggested use of surface water from TGR for drinking water purposes is a valid option. Current treatment methods, however, do not seem to be efficient since organic pollutants were detected in significant concentrations in purified tap water.     

Concentrations of perfluorinated acids in livers of birds from Japan and Korea

Livers of birds collected from Japan and Korea (n = 83) were analyzed to determine the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (FOSA), perfluorooctanoic acid (PFOA) and perfluorohexanesulfonate (PFHS). PFOS was found in the livers of 95% of the birds analyzed at concentrations greater than the limit of quantitation (LOQ) of 10 ng/g, wet weight. The greatest concentration of PFOS of 650 ng/g, wet weight, was found in the liver of a common cormorant from the Sagami River in Kanagawa Prefecture. Concentrations of PFOS in bird livers from Japan and Korea were within the ranges of values reported for those from the United States and certain European countries. PFOA and PFHS were found in 5-10% of the samples analyzed. The greatest concentrations of PFOA and PFHS in bird livers were 21 and 34 ng/g, wet weight, respectively. FOSA was found in all the samples (n = 10) of cormorants collected from the Sagami River in Japan. The greatest concentration of FOSA in cormorant liver was 215 ng/g, wet weight. There was no significant correlation between the concentrations of PFOS and FOSA in cormorants collected from the Sagami River. These results suggested that the distribution of FOSA is localized. No age- or gender-specific differences in fluorochemical concentrations could be discerned in birds.     

Particulate organic matter in the sea: the composition conundrum

As organic matter produced in the euphotic zone of the ocean sinks through the mesopelagic zone, its composition changes from one that is easily characterized by standard chromatographic techniques to one that is not. The material not identified at the molecular level is called "uncharacterized". Several processes account for this transformation of organic matter: aggregation/disaggregation of particles resulting in incorporation of older and more degraded material; recombination of organic compounds into geomacromolecules; and selective preservation of specific biomacromolecules. Furthermore, microbial activities may introduce new cell wall or other biomass material that is not easily characterized, or they may produce such material as a metabolic product. In addition, black carbon produced by combustion processes may compose a fraction of the uncharacterized organic matter, as it is not analyzed in standard biochemical techniques. Despite these poorly-defined compositional changes that hinder chemical identification, the vast majority of organic matter in sinking particles remains accessible to and is ultimately remineralized by marine microbes.     

Tidal salt marsh sediment in California, USA. Part 1: occurrence and sources of organic contaminants

Surface sediment samples (0-5 cm) from five tidal marshes along the coast of California, USA were analyzed for organic pollutants to investigate their relationship to land use, current distribution within marshes, and possible sources. Among the study areas, Stege Marsh, located in San Francisco Bay, was the most contaminated. Compared to San Francisco Bay, Stege Marsh had much higher levels of organic contaminants such as PCBs (polychlorinated biphenyls), DDTs, and chlordanes. At reference marshes (Tom's Point and Walker Creek in Tomales Bay), organic contaminants in sediments were very low. While PAHs (polycyclic aromatic hydrocarbons) were found at all of the study areas (22-13,600 ng g(-1)), measurable concentrations of PCBs were found only in the sediments from Stege Marsh (80-9,940 ng g(-1)). Combustion related (pyrogenic) high molecular weight PAHs were dominant in sediments from Stege and Carpinteria Marshes, while in sediments from Tom's Point and Walker Creek petroleum related (petrogenic) low molecular weight PAHs and alkyl-substituted PAHs were much more abundant than pyrogenic PAHs. PCB congener patterns in all of the Stege Marsh samples were the same and revealed that Aroclor 1248 was a predominant source. In all marshes, the sum of DDE and DDD accounted for more than 90% of total DDTs, indicating that DDT has degraded significantly. The ratios of p,p'-DDE to p,p'-DDD in sediments from Stege Marsh provide evidence of possible previous use of technical DDD. Chlordane ratios indicated that chlordanes have degraded slightly. Bis(2-ethylhexyl)phthalate (280-32,000 ng g(-1)) was the most abundant phthalate. The data indicates that Stege Marsh may be a source of contaminants that continue to be discharged into San Francisco Bay.     

Spatial characterization of the Baltic sea drainage basin and its unmonitored catchments

We present an updated, harmonized hydrologic base map of the entire Baltic Sea Drainage Basin (BSDB), including 634 subdrainage basins. The updated map has a level of detail approximately 5 to 10 times higher than the current standard and includes various spatial-aggregation possibilities of relevance for water management. All 634 subdrainage basins and their various spatial aggregations are characterized in terms of population, land cover, drainage density, and slope. We identify, quantify, and characterize, in particular, drainage basins that are unmonitored with regard to the combination of water-flow and nutrient-concentration measurements needed to monitor coastal nutrient and pollutant loading. Results indicate that out of a total BSDB population of 84 239 000 in 2002, 24% lived in unmonitored coastal drainage basins that cover 13% of the total BSDB area. A more detailed analysis of Swedish catchments indicates that Sweden has a particularly large proportion of unmonitored coastal catchment areas (20% of the total Swedish area) with high population pressures (55% of the total Swedish population), when compared with average conditions for the whole BSDB. In general, the investigated characteristics of unmonitored coastal basins vary and differ largely from those in adjacent monitored drainage basins within the BSDB.