Pilot scale application of a method for the analysis of perfluorinated compounds in surface soils

A growing number of studies now indicate that perfluorinated compounds (PFCs) are globally distributed in the environment. Their widespread distribution and presence in remote locations has led to questions about the importance of atmospheric and oceanic transport. Describing their distribution in surface soils is also an essential but neglected element in developing a comprehensive understanding of their occurrence in the environment. Soils are the critical link between global atmospheric and hydrologic processes where both local and distant contaminants can accumulate and be released into aquatic and terrestrial communities. Because PFC concentrations in soils will influence ground and surface water, wildlife, and crops, methods to accurately measure PFCs in soil are clearly needed. To help answer this need, we developed a method for the analysis of nine perfluorinated carboxylic acids and four perfluorinated sulfonic acids in soil. Samples from six nations (n = 10 per nation) were analyzed by LC-MS/MS to demonstrate the method performance parameters and to make preliminary observations about the occurrence of the PFCs in soils in different parts of the world. The resulting method shows acceptable performance characteristics for the target compounds in most soils while documenting the widespread occurrence of PFCs in surface soils.     

Exposure to polybrominated diphenyl ethers associated with consumption of marine and freshwater fish in Hong Kong

Concentrations of polybrominated diphenyl ethers (PBDEs) in market fish have not previously been reported in Hong Kong. Axial and ventral muscles from 10 each common species of freshwater and marine fish purchased from markets in Hong Kong were analyzed for 22 PBDEs. Among the 10 freshwater fish species, spotted snakehead (Channa maculate) contained the highest level of PBDEs in ventral muscle (130 ng g(-1) wet wt.). For marine fish, bigeye (Priacanthus macracanthus) showed significantly higher levels of PBDEs (60.7 ng g(-1)wet wt. in ventral tissue) than all other marine species. The levels of PBDEs in fish samples ranged from 0.53 to 130 ng g(-1)wetwt. The tetrabrominated congener BDE-47 and pentabrominated BDE-99 were the predominant congeners, which accounted for 27% and 30%, respectively, of the total PBDEs. Daily PBDE intake was calculated according to the different fish consumption rate for Hong Kong consumers, and the results ranged from 222 to 1198 ng day(-1) for marine fish and 403-2170 ng day(-1) for freshwater fish. The daily PBDE intake from fish reported here were higher than those reported from the United States (8.94-15.7 ng day(-1)) and Europe (14-23.1 ng day(-1)).     

Residual levels of DDTs and PAHs in freshwater and marine fish from Hong Kong markets and their health risk assessment

Axial and ventral muscle from 10 each species of freshwater and marine fish purchased from markets in Hong Kong were analyzed for dichlorodiphenyltrichloroethane (total DDTs including DDE, DDD and DDT) and polycyclic aromatic hydrocarbons (PAHs). Among the 10 freshwater fish species, rice field eel (Monopterus albus) showed significantly higher levels of DDTs in both ventral (125 ng/g wet wt) and axial muscle (127 ng/g wet wt) than the other species. The highest concentration of PAHs was detected in catfish (Clarias fuscus), with 24.8 ng/g in ventral muscle and 9.1 ng/g in axial muscle. As to marine fish, snubnose pompano (Trachinotus blochii) showed significantly higher levels of DDT and its metabolites (1018 ng/g in ventral and 409 ng/g wet wt in axial tissues) than all other marine fish species. The overall concentrations of PAHs in marine fish species were 15.5-57.0 ng/g (axial muscle) and 18.1-118 ng/g wet wt (ventral muscle) where yellow seafin (Acanthopeyrus latus) and golden threadfin bream (Nemipterus virgatus) exhibited the highest concentrations of PAHs in the axial and ventral muscles, respectively. In general, results showed that levels of PAHs in Hong Kong market fish was low and do not expect to cause any concern for human consumption. However, the levels of DDTs in fish samples ranged from 1.10 to 1018 ng/g wet wt, and based on a fish consumption rate of 142.2g/day to calculate the screening value of 14.4 ng/g wet wt for human consumption (USEPA, 2000. Guidance for assessing chemical contaminant, data for use in fish advisories, vol. 1: fish sampling and analysis, third ed. EPA 823-R-95-007. Office of Water, Washington, DC), there were 9 out of 20 (45%) muscle samples of freshwater fish species and 14 out of 20 (70%) muscle samples of marine fish species had elevated levels of DDTs exceeded the screening value. It was also suggested to use ventral muscle for detecting concentrations of persistent organic pollutants in fish.     

Assessment of risk to humans of bisphenol A in marine and freshwater fish from Pearl River Delta, China

Bisphenol A (BPA) is a high production-volume chemical used in the manufacture of a wide variety of consumer products. However it is also a ubiquitous contaminant that can interfere with endocrine systems of wildlife and humans. China is the “world factory” and the Pearl River Delta is the major manufacturing center and is consequently polluted. Concentrations of BPA in meats of marketable fish had not been previously reported for this region. In the study upon which we report here concentrations of BPA were determined in 20 common species of freshwater and marine fish, collected from markets in Hong Kong, SAR, China. A comprehensive analytical method based on SPE extraction and liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was developed, validated and applied. The method limit of detection (LOD) and limit of quantification (LOQ) were 0.5 and 1.25 ng g⁻¹ dw, respectively. BPA was detected in 19 species of fish at concentrations, ranging from 0.5 to 2.0 ng g⁻¹ ww. Average daily BPA intake per person ranged from 1.1 × 10² ng d⁻¹ for marine fish and 2.2 × 10² ng d⁻¹ for freshwater fish. Concentrations of BPA in fish from Hong Kong markets unlikely would be causing adverse population-level effects in humans.     

Perfluorochemicals in wastewater treatment plants and sediments in Hong Kong

The study reported in this paper examined the concentrations of nineteen perfluorochemicals (PFCs), including perfluoroalkyl sulfonates, carboxylates, and sulfonamides in samples collected from Hong Kong wastewater treatment plants (WWTPs) and sediments. The study was the first to use an external isolator column to assist in the quantification of PFCs in environmental samples without having to make internal modifications to a liquid chromatography system. Perfluorooctanesulfonate was found to be the dominant PFC pollutant in Hong Kong, and the WWTP sludge was the major sink of PFCs discharged from the urban areas. Compared to discharge influenced by industrial activities, much less perfluorooctanoate was found in waste streams. The significantly lower level of perfluorodecanesulfonate in WWTP sludge reflects the important influence of consumer products on PFC distribution. The dominance of even-chain length perfluoroalkyl carboxylates in all of the WWTP sludge samples investigated further suggests the strong aerobic degradation of fluorotelomer alcohols in WWTPs.     

Exposure assessment for trace elements from consumption of marine fish in Southeast Asia

Concentrations of 20 trace elements were determined in muscle and liver of 34 species of marine fish collected from coastal areas of Cambodia, Indonesia, Malaysia and Thailand. Large regional difference was observed in the levels of trace elements in liver of one fish family (Carangidae): the highest mean concentration was observed in fish from the Malaysian coastal waters for V, Cr, Zn, Pb and Bi and those from the Java Sea side of Indonesia for Sn and Hg. To assess the health risk to the Southeast Asian populations from consumption of fish, intake rates of trace elements were estimated. Some marine fish showed Hg levels higher than the guideline values by U.S. Environmental Protection Agency and Joint FAO/WHO Expert Committee on Food Additives (JECFA). This suggests that consumption of these fish may be hazardous to the people.     

Phthalates and perfluorinated alkylated substances in Atlantic bluefin tuna (Thunnus thynnus) specimens from Mediterranean Sea (Sardinia,Italy): Levels and risks for human consumption

Atlantic blue fin tuna (Thunnus thynnus) is a species of great importance for Mediterranean Sea area, from both ecological and commercial points of view. The scientific literature reports few data on the contamination of this fish by emerging organic compounds such as perfluorinated alkylated substances(PFASs) and phthalates, being the latter never been studied in tuna. This study therefore investigated the presence of the PFASs perfluorooctane sulphonate (PFOS) and perfluoroctanoic acid (PFOA) and the phthalate di-2-ethylhexyl phthalate (DEHP), also monitored by its metabolite mono-2-ethylhexyl phthalate(MEHP), to assess both the state of contamination of Atlantic bluefin tuna specimen and the risk due to the toxicity of these compounds for human consumption. While PFOA was never found, detectable levels of PFOS (0.4–1.88 ng/g), DEHP (9–14.62 ng/g) and MEHP (1.5–6.30 ng/g) were found. The results were elaborated relating the accumulation to the size and age of the individuals and showed a correlation between the levels of different pollutants investigated.     

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Perfluorinated compounds in water, sediment, soil and biota from estuarine and coastal areas of Korea

Soil, sediment, water, and biota collected from the western coast of Korea were analyzed to determine occurrence and sources of perfluorinated compounds (PFCs). PFCs were significantly concentrations of PFCs were measured in some water and biological samples, while concentrations of PFCs in soils and sediments were relatively low. The most widely detected compound was found to be perfluorooctanesulfonate (PFOS), with a maximum concentration in water of 450 ng/L and in fish of 612 ng/g, dw. PFOS concentrations in water and biota were both less than those thought to cause toxicity. However, in both cases concentrations were within a factor of 10 of the toxicity threshold concentration. Concentrations of PFCs were significantly greater downstream than those upstream on the same river, suggesting point sources. Overall, the detection of PFCs at relatively great concentrations in various environmental matrixes from this region of Korea suggests that further studies characterizing PFCs and their potential risk to both humans and wildlife are needed.     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.     

Identification of microcystins from three collection strains of Microcystis aeruginosa

Microcystins (MCs) are toxic cyclic heptapeptides produced by various cyanobacteria genera, especially Microcystis. We identified 10 out of 12 MCs produced by three Microcystis aeruginosa strains from cyanobacteria collections, UTEX 2666, UTEX 2670 and UAM 1303, by using two analytical methods: Matrix-assisted Laser Desorption Ionization Time of Flight Mass Spectrometry (MALDI-TOF/MS) and HPLC Photodiode Array Detector coupled to a hybrid Quadrupole Time of Flight Mass Spectrometry (HPLC-PDA-QTOF/MS). MALDI-TOF/MS failed to detect non-polar MCs, such as MC-LY and MC-LW. HPLC-QTOF/MS permitted the accurate identification of most MCs present in methanolic extracts. Besides, three new MCs, namely: [D-Glu(OCH₃)⁶, D-Asp³] MC-LAba, MC-YL and MC-YM were detected by HPLC-QTOF/MS.     

Determinations of hexabromocyclododecane (HBCD) isomers in channel catfish, crayfish, hen eggs and fish feeds from China by isotopic dilution LC-MS/MS

HBCD is widely used brominated flame retardant, which is increasingly reported in the environment. A new isotopic dilution LC-MS/MS method was developed to determine three HBCD isomers, α-, β- and γ-HBCD in channel catfish, crayfish, hen eggs and fish feeds in this study, and especially for the first time HBCD isomers composition in crayfish, hen eggs and fish feeds. Soxhlet extractor and GPC cleanup were used, some important steps and crucial parameters were modified and intensified compared with other literatures, and LC and MS/MS conditions were optimized. The limits of quantitation values of 0.01, 0.005 and 0.005 ng g⁻¹ wet weight in channel catfish and crayfish were calculated for three HBCD isomers, respectively; so did 0.1, 0.05 and 0.05 ng g⁻¹ wet weight in eggs and 0.2, 0.1, 0.1 ng g⁻¹ wet weight in fish feeds. Recoveries of α-HBCD, β-HBCD and γ-HBCD were ranged between 75% and 105% for these productions at medium and high-level spiked samples, and between 60% and 85% at low-level spiked samples. The established methods were therefore suitable for the determinations of three HBCD isomers in these productions at trace contamination levels. Moreover, thirty commercial channel catfish, crayfish, hen eggs and fish feeds samples collected from local markets, and thirty home-produced hen eggs from private owners in Hubei province of China, were analyzed to determine whether these productions were contaminated by HBCD. Using the established methods, HBCD emerged in 4 of 30 fish feeds and 3 of 30 home-produced eggs, and in low-ng g⁻¹ wet weight.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Progestagens for human use, exposure and hazard assessment for the aquatic environment

Little information is available on the environmental occurrence and ecotoxicological effects of pharmaceutical gestagens released in the aquatic environment. Since eighteen different gestagens were found to be used in France, preliminary exposure and hazard assessment were done. Predicted environmental concentrations (PECs) suggest that if parent gestagens are expected to be found in the ng l⁻¹ range, some active metabolites could be present at higher concentrations, although limited data on metabolism and environmental fate limit the relevance of PECs. The biological effects are not expected to be restricted to progestagenic activity. Both anti-androgenic activity (mainly for cyproterone acetate, chlormadinone acetate and their metabolites) and estrogenic activity (mainly for reduced metabolites of levonorgestrel and norethisterone) should also occur. All these molecules are likely to have a cumulative effect among themselves or with other xenoestrogens. Studies on occurrence, toxicity and degradation time are therefore needed for several of these compounds.     

Environmental and human health risk assessment of organic micro-pollutants occurring in a Spanish marine fish farm

In this work the risk posed to seawater organisms, predators and humans is assessed, as a consequence of exposure to 12 organic micro-pollutants, namely metronidazole, trimethoprim, erythromycin, simazine, flumequine, carbaryl, atrazine, diuron, terbutryn, irgarol, diphenyl sulphone (DPS) and 2-thiocyanomethylthiobenzothiazole (TCMTB). The risk assessment study is based on a 1-year monitoring study at a Spanish marine fish farm, involving passive sampling techniques. The results showed that the risk threshold for irgarol concerning seawater organisms is exceeded. On the other hand, the risk to predators and especially humans through consumption of fish is very low, due to the low bioconcentration potential of the substances assessed.     

Health risk assessment for consumption of fish originating from ponds near Dabaoshan mine, South China

Mining effluents are a potential source of toxic metals in the surrounding aquatic ecosystem and pose a potential health risk to humans from fish consumption. The objective of this paper is to assess the impact of the long-term Dabaoshan mining operation on heavy metal accumulation in different fish species. Heavy metal accumulation (lead (Pb), cadmium (Cd), zinc (Zn), and copper (Cu)) in four tissues (liver, muscle, intestine, and gills) of five carp species (Hypophthalmichthys molitrix, Ctenopharyngodon idellus, Megalobrama amblycephala, Aristichthys nobilis, and Carassius auratus auratus) from two fishponds exposed to effluent waters from Dabaoshan mine, South China. The bioaccumulation factor (BAF) and target hazard quotients were calculated to assess potential health risks to local residents through fish consumption. Levels of heavy metals varied depending on the analyzed tissues. C. auratus auratus accumulated the higher Pb, Cd, Zn, and Cu in the intestine compared with other fish species. Liver of all five species contained high concentrations of Pb, Cd, Zn, and Cu. The BAF for the studied metals showed a descending order of Cd?>?Zn?>?Cu?>?Pb for fishpond 1 and Zn?>?Cd?>?Cu?>?Pb for fishpond 2. Risk assessments suggested that potential human health risk may be present due to high Pb and Cd concentration in the muscle of some fish species exceeding the national and international limits, although the target hazard quotients were less than one.     

Determination and health risk assessment of enrofloxacin,flumequine and sulfamethoxazole in imported Pangasius catfish products in Thailand

The goals of this study were to determine the levels of three antibiotics – enrofloxacin, flumequine and sulfamethoxazole – in Pangasius catfish products imported into Thailand and to assess the health risks from consumption. To extract these antibiotic residues, acetonitrile, methanol and a small amount of formic acid were used as solvents. Determination of the antibiotics after extraction steps was carried out by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) technique. The results showed that 14 and 3 samples of Pangasius catfish products were contaminated with enrofloxacin and sulfamethoxazole, respectively. No flumequine residue was found. While the concentration levels of these antibiotics in most contaminated samples were lower than the European Union (EU) standard, one sample was found to contain sulfamethoxazole at 245.91 µg kg^?1, which was higher than the EU standard (100 µg kg^?1), indicating the likelihood that some contaminated freshwater fish products are widely distributed in Thai markets. Notably, the concentration levels of enrofloxacin in samples of Pangasius catfish with skin were higher than in non-skin products, suggesting that products with skin might retain more antibiotic residues than non-skin products. Although the hazard quotient showed that consuming imported Pangasius catfish products, based on the current consumption rate, will not adversely affect consumer health, antibiotic residues in Pangasius catfish products imported into Thailand should be continually monitored.     

Screening of pharmaceuticals and hormones at the regional scale, in surface and groundwaters intended to human consumption

As part of a regional screening to evaluate the risk, for the health of populations, to certain classes of emerging substances, several families of pharmaceuticals and hormones were looked for in waters intended to drinking. Thus, 52 substances were investigated in 71 surface waters and 70 groundwaters. Results indicate that no water was free of pollutants, regardless of its origin (surface or groundwater) and the season of collect. The pharmaceuticals most frequently detected and with the highest concentration levels were salicylic acid, carbamazepine and acetaminophen. Among hormones, testosterone, androstenedione and progesterone were detected in almost all the samples. Globally the groundwaters were less contaminated than surface waters in regards pharmaceuticals frequencies and levels. On the other side, androgens and progestagens were present with comparable frequencies and levels in both compartments. The risk linked to the presence of these substances on human health is discussed.     

Polybrominated, polychlorinated and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans and dioxin-like polychlorinated biphenyls in marine surface sediments from Hong Kong and Korea

In this study we investigated occurrences and distribution patterns of dioxin-related compounds (DRCs) such as polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs), polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in marine surface sediments collected from the coastal waters of Hong Kong and Korea. In most sampling sites, concentrations of PCDDs were the highest, followed by DL-PCBs, PCDFs, PBDFs, PBDDs, MoBPCDDs and MoBPCDFs in this order. Levels of PBDD/Fs were generally 1-2 orders of magnitude lower than chlorinated analogues. Levels of PCDDs are higher than PCDFs in Hong Kong while levels of PBDFs are higher than PBDDs in Korea (p < 0.05). Report of PBDD/Fs and MoBPCDD/Fs in sediments from East Asian countries is novel and original. Environmental levels of PBDD/Fs are supposed to start increasing in accordance with rising production, use and disposal of brominated flame retardants (BFRs) and recycling processes of e-waste in Asian developing countries.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).