Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain)

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ng L⁻¹ range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals > alkylphenols > pesticides > illicit drugs ? estrogens.     

Detection limits can influence the interpretation of pesticide monitoring data in Canadian surface waters

Water quality monitoring programs rely on residue data that are frequently left censored, due to some observations occurring below the Method Detection Limit (MDL). Our objective was to determine the influence the MDL has on the interpretation of pesticide residues in surface waters. Water samples from tributaries in southern and central Ontario were collected by Environment Canada from 2003 to 2008 and were analyzed for 27 pesticides, with MDLs that averaged 7.02 ng⁻¹ L (range 0.39-25.1 ng⁻¹ L). We then simulated MDLs ranging from 25 to 1700 ng⁻¹ L, to determine the impact this would have on the reporting of pesticide concentrations and detections. The mean number of pesticides detected simultaneously declined with increasing, i.e. less sensitive MDLs, from 5.02 pesticides (native MDL) to 0.08 pesticides detected (MDL < 1700 ng⁻¹ L). We compared the proportion of sites where pesticides were detected in surface waters under five MDL scenarios for 13 selected pesticides. The proportions decreased sharply with increasing MDLs. We calculated detection probabilities in an effort to compensate for higher MDLs using maximum likelihood; while adjusting for detection probabilities generally improved estimates of the presence of pesticides, as the MDLs increased the ability to compensate for detection probabilities deteriorated and became unviable at high MDLs. Depending on the method of substitution for observations below MDL (replacement with ½ × or 0 × MDL), the mean and median pesticide residues became increasingly over- and underestimated, respectively, at higher MDLs. Although monitoring programs that are focused on exceedences of water quality guidelines may not require low MDLs, the achievable goals of monitoring programs oriented towards other ecological and toxicological objectives may be limited by higher MDLs.     

Determination of organochlorine pesticide residue in sediment and water from the Densu river basin, Ghana

The distribution of organochlorine pesticides in the aquatic ecosystem from the Densu river revealed varying levels of concentration in water and the sediment samples. Three locations were sampled along the river to evaluate the levels of organochlorine pesticide residue in the river. Sediment and surface water samples were extracted by soxhlet and liquid-liquid extraction respectively and analyzed using Gas Chromatograph coupled with electron capture detector. The detectable organochlorine pesticides were gamma-hexachlorocyclohexane (HCH), delta-hexachlorocyclohexane, heptachlor, aldrin and dieldrin. The other pesticides that were investigated are gamma-chlordane, alpha endosulfan, endosulfan sulfate, p,p′-DDT and its metabolite p,p′-DDE, methoxychlor, endrin and its metabolite endrin aldehyde and endrin ketone. The order of increasing frequency of detection of samples was higher in sediment than water. In sediment, the mean concentration ranged from 0.030 μg kg⁻¹ dry weight (endrin) to 10.98 μg kg⁻¹ dry weight (aldrin). The highest detected concentration of organochlorine in water was endosulfan sulfate with mean concentration of 0.185 μg L⁻¹. Analysis of variance indicated significant differences for most organochlorine pesticide residue in the sediment sampled from the various locations. Some of the levels of organochlorine pesticides detected in water were relatively high compared to guideline values set by World Health Organization and Australia and thus could be harmful if the trend is not checked.     

Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China

This study investigated the presence and distribution of 22 antibiotics, including eight quinolones, nine sulfonamides and five macrolides, in the water, sediments, and biota samples from Baiyangdian Lake, China. A total of 132 samples were collected in 2008 and 2010, and laboratory analyses revealed that antibiotics were widely distributed in the lake. Sulfonamides were the dominant antibiotics in the water (0.86-1563 ng L⁻¹), while quinolones were prominent in sediments (65.5-1166 μg kg⁻¹) and aquatic plants (8.37-6532 μg kg⁻¹). Quinolones (17.8-167 μg kg⁻¹) and macrolides [from below detection limit (BDL) to 182 μg kg⁻¹] were often found in aquatic animals and birds. Salvinia natans exhibited the highest bioaccumulation capability for quinolones among three species of aquatic plants. Geographical differences of antibiotic concentrations were greatly due to anthropogenic activities. Sewage discharged from Baoding City was likely the main source of antibiotics in the lake. Risk assessment of antibiotics on aquatic organisms suggested that algae and aquatic plants might be at risk in surface water, while animals were likely not at risk.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.     

Efficient degradation of organic pollutants with ferrous hydroxide colloids as heterogeneous Fenton-like activator of hydrogen peroxide

The capacity of a full-scale reclamation pond-constructed wetland (CW) system to eliminate 27 emerging contaminants (i.e. pharmaceuticals, sunscreen compounds, fragrances, antiseptics, fire retardants, pesticides, and plasticizers) and the seasonal occurrence of these contaminants is studied. The compounds with the highest concentrations in the secondary effluent are diclofenac, caffeine, ketoprofen, and carbamazepine. The results show that the constructed wetland (61%) removes emerging contaminants significantly more efficiently than the pond (51%), presumably due to the presence of plants (Phragmites and Thypa) as well as the higher hydraulic residence time (HRT) in the CW. A greater seasonal trend to the efficient removal of these compounds is observed in the pond than in the CW. The overall mass removal efficiency of each individual compound ranged from 27% to 93% (71% on average), which is comparable to reported data in advanced treatments (photo-fenton and membrane filtration). The seasonal average content of emerging contaminants in the river water (2488 ng L⁻¹) next to the water reclamation plant is found to be higher than the content in the final reclaimed water (1490 ng L⁻¹), suggesting that the chemical quality of the reclaimed water is better than available surface waters.     

Persistent organic pollutants associated to water fluxes and sedimentary processes in the Colorado River delta, Baja California, México

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in sediment cores from two distinctive modern channels of the Colorado River (CR) delta. Their abundance and temporal changes are associated with flood-flows from the CR across the USA-Mexico border. The CR channel is directly exposed to river flood-flows while the Hardy River (HR) is a local channel derived mainly from agricultural runoff, geothermal effluents, and treated urban wastewater. Different headwater compositions and degrees of exposure to flood-flows appear to be the factors controlling the composition of persistent organic pollutants (POPs). Enrichment of OCPs (46 ng g⁻¹ dwt in HR and 4.37 ng g⁻¹ dwt in CR) occurred during or a few years after flooding. PCB-138 (4.2 ng g⁻¹ dwt) is enriched in HR suggesting its origin in dielectric oils from the geothermal power plant. PCB-28 (2.1 ng g⁻¹ dwt) in CR may be related with atmospheric input and/or re-deposition of upstream sediments. In surficial sediments (0-3 cm), only HR exceeds international sediment quality guidelines (4,4′-DDE = 8.16 ng g⁻¹ dwt and ΣDDT = 8.34 ng g⁻¹ dwt).     

Levels of organochlorine pesticides and polychlorinated biphenyls in the critically endangered Iberian lynx and other sympatric carnivores in Spain

Accumulation of organochlorine compounds is well studied in aquatic food chains whereas little information is available from terrestrial food chains. This study presents data of organochlorine levels in tissue and plasma samples of 15 critically endangered Iberian lynx (Lynx pardinus) and other 55 wild carnivores belonging to five species from three natural areas of Spain (Doñana National Park, Sierra Morena and Lozoya River) and explores their relationship with species diet. The Iberian lynx, with a diet based on the consumption of rabbit, had lower PCB levels (geometric means, plasma: <0.01 ng mL⁻¹, liver: 0.4 ng g⁻¹ wet weight, fat: 87 ng g⁻¹ lipid weight) than other carnivores with more anthropic and opportunistic foraging behavior, such as the red fox (Vulpes vulpes; plasma: 1.11 ng mL⁻¹, liver: 459 ng g⁻¹, fat: 1984 ng g⁻¹), or with diets including reptiles at higher proportion, such as the Egyptian mongoose (Herpestes ichneumon; plasma: 7.15 ng mL⁻¹, liver: 216 ng g⁻¹, fat: 540 ng g⁻¹), or the common genet (Genetta genetta; liver: 466 ng g⁻¹, fat: 3854 ng g⁻¹). Chlorinated pesticides showed interspecific variations similar to PCBs. Organochlorine levels have declined since the 80s in carnivores from Doñana National Park, but PCB levels are still of concern in Eurasian otters (Lutra lutra; liver: 3873-5426 ng g⁻¹) from the industrialized region of Madrid.     

Molecular characterization of conjugative plasmids in pesticide tolerant and multi-resistant bacterial isolates from contaminated alluvial soil

A total of 35 bacteria from contaminated soil (cultivated fields) near pesticide industry from Chinhat, Lucknow, (India) were isolated and tested for their tolerance/resistance to pesticides, heavy metals and antibiotics. Bacterial isolates were identified by 16S rDNA sequencing. Gas Chromatography analysis of the soil samples revealed the presence of lindane at a concentration of 547 ng g⁻¹ and α-endosulfan and β-endosulfan of 422 ng g⁻¹ and 421 ng g⁻¹ respectively. Atomic Absorption Spectrophotometry analysis of the test sample was done and Cr, Zn, Ni, Fe, Cu and Cd were detected at concentrations of 36.2, 42.5, 43.2, 241, 13.3 and 11.20 mg kg⁻¹ respectively. Minimum inhibitory concentrations of all the isolates were determined for pesticides and heavy metals. All the multi-resistant/tolerant bacterial isolates were also tested for the presence of incompatibility (Inc) group IncP, IncN, IncW, IncQ plasmids and for rolling circle plasmids of the pMV158-family by PCR. Total community DNA was extracted from pesticide contaminated soil. PCR amplification of the bacterial isolates and soil DNA revealed the presence of IncP-specific sequences (trfA2 and oriT) which was confirmed by dot blot hybridization with RP4-derived DIG-labelled probes. Plasmids belonging to IncN, IncW and IncQ group were neither detected in the bacterial isolates nor in total soil DNA. The presence of conjugative or mobilizable IncP plasmids in the isolates indicate that these bacteria have gene transfer capacity with implications for dissemination of heavy metal and antibiotic resistance genes. We propose that IncP plasmids are mainly responsible for the spread of multi-resistant bacteria in the contaminated soils.     

Occurrence of glucocorticogenic activity in various surface waters in The Netherlands

Considering the important role that surface waters serve for drinking water production, it is important to know if these resources are under the impact of contaminants. Apart from environmental pollutants such as pesticides, compounds such as (xeno)estrogens have received al lot of research attention and several large monitoring campaigns have been carried out to assess estrogenic contamination in the aquatic environment. The introduction of novel in vitro bioassays enables researchers to study if – and to what extent – water bodies are under the impact of less-studied (synthetic) hormone active compounds. The aim of the present study was to carry out an assessment on the presence and extent of glucocorticogenic activity in Dutch surface waters that serve as sources for drinking water production. The results show glucocorticogenic activity in the range of <LOD – 2.4 ng dexamethasone equivalents L⁻¹ (dex EQs) in four out of eight surface waters. An exploratory time-series study to obtain a more complete picture of the yearly average of fluctuating glucocorticogenic activities at two sample locations demonstrated glucocorticogenic activities ranging between <LOD – 2.7 ng dex EQs L⁻¹. Although immediate human health effects are unlikely, the environmental presence of glucocorticogenic compounds in the ng L⁻¹ range compels further environmental research and assessment.     

Contamination by chlorinated pesticides, PCBs and PBDEs in Atlantic spotted dolphin (Stenella frontalis) in western South Atlantic

Chlorinated pesticides, PCBs and PBDEs were analysed in nine blubber samples of Atlantic spotted dolphins, Stenella frontalis, incidentally captured during fishing operations in southern and southeastern Brazil between 2005 and 2007. The majority of compounds analysed were detected, suggesting widespread contamination over the region. Although the samples came from a location far from main coastal industrial areas, the results revealed an influence from such sources. Therefore, levels of PCBs (774-23 659 ng g⁻¹ lipid wt.) and PBDEs (23-1326 ng g⁻¹ lipid wt.) detected seem to be related to the movement of individuals throughout near-shore and offshore waters. The sample from a lactating female exhibited a lower level of contamination and a distinct pattern, indicating selective transfer favouring less lipophilic compounds.     

Simultaneous determination of organochlorine pesticides and bisphenol A in edible marine biota by GC-MS

A study to assess the level of organochlorine pesticides (OCPs) and bisphenol A (BPA) in edible marine biota collected from coastal waters of Malaysia was conducted using GC-MS and SPE extraction. An analytical method was developed and validated to measure the level of 15 OCPs and BPA simultaneously from five selected marine species. It was observed that some samples had low levels of p,p′-DDE, p,p′-DDT and p,p′- DDD ranging from 0.50 ng g⁻¹ to 22.49 ng g⁻¹ dry weight (d.w) but significantly elevated level of endosulfan I was detected in a stingray sample at 2880 ng g⁻¹ d.w. BPA was detected in 31 out of 57 samples with concentration ranging from below quantification level (LOQ: 3 ng g⁻¹) to 729 ng g⁻¹ d.w. The presence of OCPs is most likely from past use although there is also indication of illegal use in recent times. The study also reveals that BPA is more widely distributed in coastal species caught off the coast of the most developed state. The potential health risk from dietary intakes of OCPs and BPA from the analysed fish species was negligible.     

Concentrations of organochlorine pesticides and 2,4,6-trichloroanisole in cork bark

Organochlorine pesticides are persistent lipophilic organic pollutants and tend to accumulate in growing plants. During growth, cork is in contact with the open air for long periods (9-12 years). Owing to the previous widespread use of organochlorine pesticides and their high persistence in the environment, there is a risk that residues of such pesticides may be present in cork.In this study, the concentrations of 14 organochlorine pesticides—all of which are indicators of environmental pollution—were analyzed in cork bark samples from three regions in Spain and one in Portugal. In addition, the concentrations of 2,4,6-trichlorophenol (TCP) and 2,4,6-trichloroanisole (TCA) were also analyzed.Our results show only very low concentrations of lindane, γ-HCH (<2.6 ng g⁻¹) and its byproducts α-HCH (<3.5 ng g⁻¹) and β-HCH (<0.6 ng g⁻¹).Among the DDT and its metabolites, only two were found: p,p′-DDT was found in a cork sample from Extremadura (0.1 ng g⁻¹) and p,p′-DDE was present at a maximum concentration of 2.9 ng g⁻¹ in a cork sample from Castile-La Mancha. However, all concentrations were well below the legal limit established by Regulation (EC) No. 396/2005 (10 ng g⁻¹ in foodstuffs). We can conclude, therefore, that the cork samples we studied complied with food safety standards.     

Phyt'Eaux Cités: application and validation of a programme to reduce surface water contamination with urban pesticides

This paper presents first results of Phyt’Eaux Cités, a program put in place by the local water supply agency, the SEDIF (Syndicat des Eaux d’Ile-de-France), in collaboration with 73 local authorities, private societies and institutional offices (365 km²). The challenges included: measurement of the previous surface water contamination, control of urban pesticide applications, prevention of pesticide hazard on users and finally a overall reduction of surface water contamination. An inquiry on urban total pesticide amount was coupled with a surface water bi-weekly monitoring to establish the impact of more than 200 molecules upon the Orge River. For 2007, at least 4400 kg and 92 type of pesticides (essentially herbicides) were quantified for all urban users in the Phyt’Eaux Cités perimeter. At the outlet of the Orge River (bi-weekly sampling in 2007), 11 molecules were always detected above 0.1 μg L⁻¹. They displayed the mainly urban origin of pesticide surface water contamination. Amitrole, AMPA (Aminomethyl Phosphonic Acid), demethyldiuron, diuron, glyphosate and atrazine were quantified with a 100% of frequency in 2007 and 2008 at the Orge River outlet. During the year, peaks of contamination were also registered for MCCP, 2,4 MCPA, 2,4 D, triclopyr, dichlorprop, diflufènican, active substances used in large amount in the urban area. However, some other urban molecules, such as isoxaben or flazasulfuron, were detected with low frequency. During late spring and summer, contamination patterns and load were dominated by glyphosate, amitrole and diuron, essentially applied by cities and urban users. Both isoproturon and chlortoluron were quantified during autumn and winter months according to upstream agricultural practices. In conclusion, 3 years after the beginning of this programme, the cities reduced the use of 68% of the total pesticide amount. An improvement on surface water quality was found from 2008 and during 2009 for all pesticides. In particular, glyphosate showed a decrease of the load above 60% in 2008, partly related to the Phyt’Eaux Cités action.     

Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003

In Malaysia, rivers are the main source of public water supplies. This study was conducted from 2002 to 2003 to determine the levels of selected organochlorine and organophosphate pesticides in the Selangor River in Malaysia. Surface water samples have been collected seasonally from nine sites along the river. A liquid-liquid extraction followed by gas chromatography-mass spectrometry technique was used to determine the trace levels of these pesticide residues. The organochlorine pesticides detected were lindane, heptachlor, endosulfan, dieldrin, endosulfan sulfate, o,p'-DDT, p,p'-DDT, o,p'-DDE and p,p'-DDE whereas for organophosphate pesticides, they were chlorpyrifos and diazinon. At the river upstream where a dam is located for public water supply, incidents of pesticide levels exceeding the European Economic Community Directive of water quality standards have occurred. Furthermore, the wetland ecosystems located at the downstream of the river which houses the fireflies community is being threatened by occasional pesticide levels above EPA limits for freshwater aquatic organisms. The occurrence of these residual pesticides in the Selangor River can be attributed to the intense agriculture and urban activity.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

Risk assessment of xenoestrogens in a typical domestic sewage-holding lake in China

Release of domestic sewage leads to accumulation of xenoestrogens in holding waters, especially in closed or semi-enclosed waters such as lakes. In the study, the occurrence, distribution, estrogenic activity and risk of eight xenoestreogens were evaluated in Lake Donghu, China. Nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) were identified as the main xenoestrogens ranging from tens of ng L⁻¹ (in the surface water) or ng g⁻¹ dw (in the suspended particles and sediment) to tens of μg L⁻¹ or μg g⁻¹ dw. The sum of 17β-estradiol equivalents (∑EEQs) ranged from 0.32 to 45.02 ng L⁻¹ in the surface water, 0.53 to 71.86 ng g⁻¹ dw in the suspended particles, and 0.09 to 24.73 ng g⁻¹ dw in the sediment. Diethylstilbestrol (DES) was determined as the main contributor to ∑EEQs followed by NP. The risk assessment showed a higher risk in the surface water than in the suspended particles and sediment in such domestic sewage-holding lake.     

Mercury levels and trends (1993-2009) in bream (Abramis brama L.) and zebra mussels (Dreissena polymorpha) from German surface waters

Mercury concentrations have been analysed in bream (Abramis brama L.) and zebra mussels (Dreissena polymorpha) collected at 17 freshwater sites in Germany from 1993-2009 and 1994-2009, respectively, within the German Environmental Specimen programme. Mercury concentrations in bream ranged from 21 to 881 ng g⁻¹ wet weight with lowest concentrations found at the reference site Lake Belau and highest in fish from the river Elbe and its tributaries. Statistical analysis revealed site-specific differences and significant decreasing temporal trends in mercury concentrations at most of the sampling sites. The decrease in mercury levels in bream was most pronounced in fish from the river Elbe and its tributary Mulde, while in fish from the river Saale mercury levels increased. Temporal trends seem to level off in recent years. Mercury concentrations in zebra mussels were much lower than those in bream according to their lower trophic position and varied by one order of magnitude from 4.1 to 42 ng g⁻¹ wet weight (33-336 ng g⁻¹ dry weight). For zebra mussels, trend analyses were performed for seven sampling sites at the rivers Saar and Elbe of which three showed significant downward trends. There was a significant correlation of the geometric mean concentrations in bream and zebra mussel over the entire study period at each sampling site (Pearson’s correlation coefficient = 0.892, p = 0.00002). A comparison of the concentrations in bream with the environmental quality standard (EQS) of 20 ng g⁻¹ wet weight set for mercury in biota by the EU showed that not a single result was in compliance with this limit value, not even those from the reference site. Current mercury levels in bream from German rivers exceed the EQS by a factor 4.5-20. Thus, piscivorous top predators are still at risk of secondary poisoning by mercury exposure via the food chain. It was suggested focusing monitoring of mercury in forage fish (trophic level 3 or 4) for compliance checking with the EQS for biota and considering the age dependency of mercury concentrations in fish in the monitoring strategy.     

Spatial distribution of perfluoroalkyl acids in the Pearl River of Southern China

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4–C11) and perfluorosulfonates (PFSAs, C4, C6–C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization–tandem mass spectrometry (HPLC/(-)ESI–MS/MS). The concentrations of total PFAAs (ΣPFAAs) ranged from 3.0 to 52 ng L⁻¹, with an average of 19 ± 12 ng L⁻¹. The highest concentrations of ΣPFAAs were detected in the surface water of the Dong Jiang tributary (17–52 ng L⁻¹), followed by the main stream (13–26 ng L⁻¹) and the Sha Wan stream (3.0–4.5 ng L⁻¹). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of ΣPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs.     

The distribution of 4-nonylphenol in marine organisms of North American Pacific Coast estuaries

One of the chemical breakdown products of nonylphenol ethoxylates, 4-nonylphenol (4-NP), accumulates in organisms and is of concern as an environmental pollutant due to its endocrine disrupting effects. We measured 4-NP levels in the seawater, sediment, and twelve organisms within the California estuary, Morro Bay, and examined biomagnification of 4-NP using stable isotope abundances (δ¹⁵N and δ¹³C) to quantify trophic position. 4-NP concentrations in organisms from Morro Bay included 25000 ± 8600 ng g⁻¹ lw in liver of California sea lion, 14000 ± 5600 ng g⁻¹ lw in liver of harbor porpoise, 138000 ± 55000 ng g⁻¹ lw in liver of sea otters, 15700 ± 3600 ng g⁻¹ lw in liver of seabirds, 36100 ± 6100 ng g⁻¹ lw in arrow goby fish, 62800 ± 28400 ng g⁻¹ lw in oysters, and 12700 ± 1300 ng g⁻¹ lw in mussels. 4-NP levels generally showed a pattern of trophic dilution among organisms in Morro Bay, with exceptions of biomagnification observed between three trophic links: mussel to sea otter (BMF 10.9), oyster to sea otter (BMF 2.2), and arrow goby to staghorn sculpin (BMF 2.7). Our examination of other west coast estuaries of USA and Canada revealed that mean 4-NP concentrations in gobies and mussels from Morro Bay were significantly higher than those from a more urbanized estuary, San Francisco Bay (goby: 11100 ± 3800 ng g⁻¹ lw) and from a remote estuary, Bamfield Inlet, Canada (goby: 9000 ± 900 ng g⁻¹ lw, mussel: 6100 ± 700 ng g⁻¹ lw). Relative to other estuaries worldwide, 4-NP levels in seawater (0.42 ± 0.16 μg L⁻¹) and sediment (53 ± 14 ng g⁻¹ dw) of Morro Bay are low, but gobies and oysters have higher 4-NP levels than comparable fauna.