Organophosphates and Synthetic Musk Fragrances in Freshwater Streams in Hessen/Germany

Four small freshwater river systems in Hessen, Germany, have been investigated with respect to seasonal and spatial concentration variations and transported load of the organophosphates tri‐n‐butyl phosphate (TBP), tris(2‐butoxyethyl)phosphate (TBEP), tris(2‐chloroethyl)phosphate (TCEP), tris(1‐chloro‐2‐propyl)phosphate (TCPP), and tris(1,3‐dichloro‐2‐propyl)phosphate (TDCPP) and the synthetic musk fragrances 1,3,4,6,7,8‐hexahydro‐4,6,6,7,8,8‐hexa‐methylcyclopenta‐[γ]‐2‐benzopyran (HHCB) and 7‐acetyl‐1,1,3,4,4,6‐hexamethyl‐1,2,3,4‐tetrahydronaphthalene (AHTN). Data originate from water samples collected in the time span from September 2003 to April 2005 at 25 sampling locations. The detection frequency for all compounds was about 90%. Mean concentration levels of organophosphates were 502 ng/L (TCPP), 276 ng/L (TBP), 183 ng/L (TBEP), 118 ng/L (TCEP), and 117 ng/L (TDCPP). The synthetic musk fragrances HHCB and ATHN were detected with mean concentrations of 141 and 46 ng/L, respectively. The variability of the concentration of all compounds was high with respect to space and time. The highest concentrations were observed in the Schwarzbach system characterized by the highest proportion of wastewater compared to the other river systems. Concentration levels of synthetic musk fragrances were significantly lower in summer times compared to winter times.     

Antifouling biocides in water and sediments from California marinas

Irgarol 1051 is a common antifouling biocide and is highly toxic to non-target plant species at low ng/L concentrations. We measured up to 254 ng/L Irgarol in water and up to 9 ng/g dry weight Irgarol in sediments from Southern California recreational marinas. Irgarol’s metabolite, M1, concentrations were up to 62 ng/L in water and 5 ng/g dry weight in sediments. Another antifouling biocide, diuron, reached up to 68 ng/L in water and 4 ng/g dry weight in sediments. The maximum Irgarol concentrations in water were greater than the Irgarol concentration recommended as the plant toxicity benchmark (136 ng/L), suggesting that Irgarol concentrations may be high enough to cause changes in phytoplankton communities in the sampled marinas. Irgarol concentrations measured in sediments were greater than calculated Environmental Risk Limits (ERLs) for Irgarol in sediments (1.4 ng/g). Antifouling pesticide accumulation in sediments may present a potential undetermined risk for benthic organisms.     

Enrichment and partitioning of polycyclic aromatic hydrocarbons in the sea surface microlayer and subsurface water along the coast of Xiamen Island,China

Sea microlayer (SML) and subsurface water (SSW) samples were collected around Xiamen Island to study the enrichment and partitioning of polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 93.43 to 411.05 ng L⁻¹ in the SML and 49.29–279.42 ng L⁻¹ in the SSW. Compared with the results of previous studies before pollution control measurements, PAHs levels decreased significantly. The enrichment factors (EFs) of dissolved and particulate PAHs varied from 0.68 to 2.71 and 0.43–3.56. EFs showed the consistent enrichment trends with sites and exhibited different enrichment characteristics between 2 and 3 ring PAHs and 4 ring PAHs. Furthermore, the much higher concentrations of BaP (strong carcinogenicity) were accompanied by higher EFs in the SML samples from the Western Xiamen Harbour, which together indicated the risk of impacts to the fish eggs that usually float on the SML water after exposure to oil spills and combustion, contributed directly by the port and shipping activities.     

Environmental behavior of organotin compounds in the coastal environment of Xiamen,China

In 2006, organotins pollution were investigated in the coastal environment of Xiamen, China. Six species of organotin compounds including tributyltin, triphenyltin and their degradation compounds were quantified in the dissolved and particulate phases of the water, and in the sediment using GC-FPD. The concentrations of organotin compounds ranged from 2.2 to 160 ng (Sn) L⁻¹ dissolved in the water, 0.14–6.7 ng (Sn) L⁻¹ in suspended particulate matter and nd ∼ 26 ng (Sn) g⁻¹ (dry weight) in the sediment. The highest concentration of total organotin or tributyltin in water was found in a shipyard and at a station near the inlet of the harbor, indicating fresh inputs of antifouling paints to Xiamen’s coastal environment. Organotin speciation was performed on sediment cores to investigate contamination trends over the past ten years in the harbor. The results of ²¹⁰Pb dating indicated that Xiamen western harbor suffered contamination during 2000. The environmental behavior of organotins such as the enhancement of the microlayer, partitioning between water/suspended particulate matter and between water/sediment are also discussed in this paper.     

Sediment PAH: Contrasting levels in the Caspian Sea and Anzali Wetland

A comparative study of 23 PAH congeners in sediment of the Caspian Sea coast and Anzali Wetland was conducted in 2010. Surface sediment was analyzed using chromatography and mass spectrometry. Total PAH concentrations ranged between 212 and 9009 ng g⁻¹ dw. Spatial distribution maps revealed that PAH levels were higher in the coastal areas of the Caspian Sea where oil related activities have been common since 1800’s. Diagnostic ratios analysis indicated that PAHs largely originated from petrogenic processes. PAH toxicity level was assessed using sediment quality guidelines and toxic equivalent concentrations to determine toxic effects on marine organism. Based on these investigations, in our study areas, the probability of toxicity for benthic organisms is “low to medium”. The toxic equivalent concentrations of carcinogenic PAHs varied between 11 and 231 ng TEQ/g; higher total toxic equivalent concentrations values were found in the coastal areas of the Caspian Sea.     

Assessment of TBT and organic booster biocide contamination in seawater from coastal areas of South Korea

Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35–1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites.     

Effects of tributyltin at concentrations below ambient levels in seawater on Caprella danilevskii (Crustacea: Amphipoda: Caprellidae)

Hatched juveniles of Caprella danilevskii (Crustacea: Amphipoda) were exposed to one of two concentrations of tributyltin (TBT) (1.1 and 10.7 ng TBT L⁻¹) for 49 d at 20 °C. These concentrations are near or below ambient levels in seawater. In both treatments and control, the survival rate was 100% at maturation, and >85% at the end of the experiments. Females reached maturation at 20 (median) to 21.5 d at instar VII, and repeated spawning 4–5 times during the experiment. The total number of juveniles per female decreased significantly from 39.5 in the control to 24.5 and 17.5 in 1.1 ng L⁻¹ and 10.7 ng L⁻¹ treatments, respectively. An earlier study reported that as the TBT concentration in seawater increased from a 0–10 ng L⁻¹ regime to a 10–20 ng L⁻¹ regime, the number of stations where Caprella spp. could be collected decreased along the coast of the Seto Inland Sea, of Japan. Thus, the present study indicates the possibility that the extremely low concentration of TBT measured in Japanese waters after 2000 lead to a reduction in reproductive success of Caprella spp.     

Content and distribution of trace metals in surface sediments from the northern Bering Sea,Chukchi Sea and adjacent Arctic areas

Concentrations of trace metals (Zn, Cr, Cu, V, Cd and Pb), total organic carbon (TOC), black carbon (BC) and their granulometry were examined in 25 surface sediment samples from the northern Bering Sea, Chukchi Sea and adjacent areas. Trace metal concentrations in the sediments varied from 21.06–168.21 mg kg⁻¹ for Zn, 8.91–46.94 mg kg⁻¹ for Cr, 2.69–49.39 mg kg⁻¹ for Cu, 32.46–185.54 mg kg⁻¹ for V, 0.09–0.92 mg kg⁻¹ for Cd, and 0.95–15.25 mg kg⁻¹ for Pb. The geoaccumulation index (I_geo) indicated that trace metal contamination (Zn and Cd) existed in some stations of the study area. The distribution of grain size plays an important role in influencing the distribution of trace metals (Zn, Cr, Cu, V, and Pb) in sediments from the Chukchi Sea and adjacent areas.     

Occurrence of endocrine-disrupting chemicals in riverine sediments from the Pearl River Delta,China

The endocrine-disrupting chemicals (EDCs) was investigated in 28 riverine sediments from the Pearl River system, China and analyzed by an ultrasonication extraction and GC–MS method. The concentrations of 4-tert-octylphenol (OP), 4-nonylphenol (NP), and bisphenol A (BPA) in the sediments were in the ranges of <2.0–210, 107–16198 and <1.7–430 ng/g dw, respectively. The steroid estrogens estrone (E1) and 17β-estradiol (E2) in the sediments ranged from <1.3 to 10.9 ng/g dw and from <0.9 to 2.6 ng/g dw, respectively. The spatial distribution of these chemicals was related to the discharge of domestic and industrial wastewater along the rivers. The positive correlation between EDCs and total organic carbon indicates that sedimentary organic carbon is an important factor in controlling the distributions of EDCs. Compared with other previous studies, the ZR and DR rivers from the PRD were heavily contaminated by APs and BPA.     

Distributions of polychlorinated biphenyls in the Daliao River estuary of Liaodong Bay,Bohai Sea (China)

The distributions of 41 polychlorinated biphenyls (PCBs) were determined in the aqueous phase, suspended particulate matter (SPM), and sediment of the Daliao River estuary in Liaodong Bay, Bohai Sea (China). The total PCB concentrations ranged from 5.51 to 40.28 ng L⁻¹ in the surface water, from 6.78 to 66.55 ng L⁻¹ dry weight in the SPM, and from 0.83 to 7.29 ng g⁻¹ dry weight in the sediment. The PCB concentrations in water, SPM, and sediment were moderate relative to those reported for other estuary and marine systems around the world. Sedimentary PCB concentrations decreased offshore due to the active deposition of laterally transported river-borne particles. The predominance of the highly chlorinated congeners for the water, SPM, and sediment samples are an indication of either a lack of degradation or the presence of nearby or recent releases into the environment.     

Total,methyl and organic mercury in sediments of the Southern Baltic Sea

Distribution of sedimentary mercury in the Southern Baltic was investigated. Sediment samples were collected from the Southern Baltic in the period from 2009 to 2011, and concentrations of sedimentary total mercury (average 102 ng/g, range 5.8–225 ng/g) and methyl mercury (average 261 pg/g, range 61–940 pg/g) were measured in the manner that the influence of both patchiness and seasonal changes were assessed. Moreover, sedimentary mercury extracted with organic solvent- the so-called organic mercury was also analyzed (average 425 pg/g, range 100–1440 pg/g). There is a statistically significant dependence between organic mercury and both methyl mercury and total mercury concentrations in the sediments. Methyl mercury contribution to total mercury varied from 0.12% to 1.05%, while organic mercury contributed to 2% of total concentration on average. The area studied, although mercury concentrations exceed threefold the geochemical background, can be regarded as moderately contaminated with mercury, and methylmercury.     

Perfluorinated compounds in surficial sediments of the Ganges River and adjacent Sundarban mangrove wetland,India

This study reports the first evidence of the quantification of two dominant perfluorinated compounds (PFCs), namely perfluorooctanesulfate (PFOS) and perfluorooctannoate (PFOA), in surface sediment samples (0–5 cm; n = 13) from the Ganges (Hugli) River including Sundarban wetland, India using HPLC–MS/MS. The concentrations of PFOA exhibited a wide range of concentrations from <0.5 to 14.09 ng/g dry wt, whereas the concentration of PFOS was always below the detection limit of <0.5 ng/g dry wt. A consistent enrichment of PFOA was recorded in all the five sites of Sundarban (mean value 11.61 ± 1.86) whereas it was of moderate concentration or below the detection level in the seven sites along with the lower stretch of the Ganges (Hugli) River estuary (mean value 5.96 ng/g dry wt ± 5.36). Wastewater and untreated effluents are likely the major causes of accumulation of PFCs in sediments. The present paper could be used as baseline study to assess future monitoring programs of the ecosystem.     

Atmospheric polychlorinated biphenyl (pcb) inputs to a coastal city near the marmara sea

Recent studies have shown that polychlorinated biphenyl (PCB) levels are high in coastal sites. Various types of deposition events, including dry deposition, air–water exchange and wet deposition, were analyzed as part of the study to illustrate the pollution level. The atmospheric levels and deposition mechanisms of 82 PCBs were investigated in Mudanya, a coastal city in Turkey. A total of 175 samples and 112 blanks were collected. Air–water exchange and particle phase dry deposition fluxes were 120 ± 90 ng/m²-d and 125 ± 160 ng/m²-d, respectively. The wet-dry deposition sampler (WDDS) consisted of two reservoirs, wet and dry. Collected with the WDDS, the dry deposition flux was 21 ± 20 ng/m²-d, and the wet deposition fluxes (during the rainy period) were 145 ± 130 ng/m²-d and 195 ± 270 ng/m²-d for the dissolved and particulate phases, respectively. Mass transfer coefficients (MTCs), dry deposition velocities and washout ratios were calculated and compared with the literature values.     

Maternal-to-fetal transfer and concentration profiles of PCB congeners for Steller sea lions (Eumetopias jubatus) from Hokkaido,Japan

The concentrations of PCB congeners in the blubber and liver of mother Steller sea lions (Eumetopias jubatus; SSLs) and their fetuses from the coast of Hokkaido, Japan in 2008, 2010 and 2012 were analyzed by HRGC–HRMS, in order to elucidate PCB congener profiles and maternal-to-fetal transfer of PCBs in SSLs. ΣPCBs in the fetuses were 1400 ± 660 (the mean ± SD) ng/g-fat in the blubber and 570 ± 320 ng/g-fat in the liver, respectively. There was a concern that SSLs had been contaminated by PCBs during the fetal period. The concentrations of the major congeners in the blubber and liver were a correlation between the fetus and mother (blubber: r = 0.9934, liver: r = 0.9160; P ≦ 0.05). The results indicated that PCBs in the fetuses came from the mothers. #177 and #199 showed no correlations between the fetus and the mother in the blubber and liver. This indicated a selective capture by some natural protector such as the placenta.     

Geochemical modelling and speciation studies of metal pollutants present in selected water systems in South Africa

Metal pollutants in water poses great threats to living beings and hence requires to be monitored regularly to avoid loss of lives. Various analytical methods are available to monitor these pollutants in water and can be improved with time. Modelling of metal pollutants in any water system helps chemists, engineers and environmentalists to greatly understand the various chemical processes in such systems. Water samples were collected from waste water treatment plant and river from highlands close to its source all the way to the ocean as it passing through areas with high anthropogenic activities. Pre-concentration of pollutants in the samples was done through acid digestion and metal pollutants were analysed using inductively coupled plasma-optical emission spectra (ICP-OES) to determine the concentration levels. Metal concentrations ranged between 0.1356–0.4658 mg/L for Al; 0.0031–0.0050 mg/L for Co, 0.0019–0.0956 mg/L for Cr; 0.0028–0.3484 mg/L for Cu; 0.0489–0.3474 mg/L for Fe; 0.0033–0.0285 mg/L for Mn; 0.0056–0.0222 mg/L for Ni; 0.0265–0.4753 mg/L for Pb and 0.0052–0.5594 mg/L for Zn. Modelling work was performed using PHREEQC couple with Geochemist’s workbench (GWB) to determine speciation dynamics and bioavailability of these pollutants. Modelling thus adds value to analytical methods and hence a better complementary tool to laboratory-based experimental studies.     

Inorganic carbon and nutrient fluxes on the Arctic Shelf

Historic data from the Russian-American Hydrochemical Atlas of Arctic Ocean together with data from the TRANSDRIFT II 1994 and TUNDRA 1994 cruises have been used to assess the spatial and inter-annual variability of carbon and nutrient fluxes, as well as air–sea CO₂ exchange in the Laptev and western East Siberian Seas during the summer season. Budget computations using summer data of dissolved inorganic phosphate (DIP), dissolved inorganic nitrogen (DIN) and dissolved inorganic carbon (DIC) gives that the Laptev Sea shelf is a net sink of DIP and DIN of 2.5×10⁶, 23.2×10⁶ mol d⁻¹, respectively, while it is a net source of DIC (excluding air–sea exchange) of 1249×10⁶ mol d⁻¹. In the East Siberian Seas the budget computations give 0.5×10⁶, −11.4×10⁶ and −173×10⁶ mol d⁻¹ (minus being a sink) for DIP, DIN, and DIC, respectively. In summers, the Laptev Sea Shelf is net autotrophic while the East-Siberian Sea Shelf is net heterotrophic, and both systems are weak net denitrifying. The Laptev Sea Shelf takes up 2.1 mmol CO₂ m⁻² d⁻¹ from atmosphere, whereas the western part of the East-Siberian Sea Shelf loose 0.3 mmol CO₂ m⁻² d⁻¹ to the atmosphere. The variability of DIP, DIN and DIC fluxes during summer in the different regions of the Laptev and East Siberian Seas depends on bottom topography, river runoff, exchange with surrounding seas and wind field.     

Contrasting key roles of Ruppia cirrhosa in a southern Mediterranean lagoon: Reservoir for both biodiversity and harmful species and indicator of lagoon health status

The distribution of Ruppia cirrhosa meadow density and its epiphytic organisms in relation with environmental factors were studied in summer 2011 at five stations in the Ghar El Melh lagoon (GML; southern Mediterranean Sea). Eleven epiphytic groups were recognised among which diatoms and dinoflagellates were the dominant groups and greatest contributors to temporal dissimilarity. An overwhelming concentrations of harmful microalgae was recorded, mainly represented by the toxic dinoflagellate Prorocentrum lima with maximal concentrations attaining 6 × 10⁵ cells 100 g⁻¹ of Ruppia fresh weight. The epifauna community accounted for only 1.4% of total epiphyte abundance and was comprised predominantly of nematodes (47.51%), ciliates (32.59%), fish eggs (7.2%) and larvae (4.95%). PERMANOVA analyses revealed a significant spatio-temporal variation of all epiphytic groups (p < 0.01). In this study, R. cirrhosa and its epiphytes were studied as potential early warning indicators of the health status of GML waters.     

Lethal and estrogenic effects of 4-nonylphenol in the cockle Cerastoderma glaucum

The lethal and sublethal effects of the xenoestrogen 4-nonylphenol (NP) were evaluated in the cockle Cerastoderma glaucum. In a 96-h lethality test, bivalves were exposed to 0, 0+ acetone, 0.19, 0.38, 0.75, 1.5 and 3.0 mg NP/l. The 96-h LC₅₀ value was 0.3 mg NP/l. No mortality was observed at 0.1 mg NP/l. The potential estrogenicity of NP was studied in both sexually undifferentiated (resting phase) and differentiated (pre-spawning phase) cockles, exposed for 7 and 14 days to 0, 0+ acetone, 0.0125, 0.025, 0.05, and 0.1 mg NP/l. Vitellogenin (Vg)-like protein levels were determined in both haemolymph and digestive gland by the alkali-labile phosphate (ALP) assay. In the resting phase, exposure for 7 days to 0.1 mg NP/l resulted in significant increases in ALP in both haemolymph and digestive gland, compared with controls. A significant increase was also observed in digestive gland of animals exposed to 0.0125 mg NP/l-exposed animals. After 14 days of exposure, haemolymph ALP levels were significantly increased in exposed animals at all NP concentrations tested, whereas no difference was recorded in digestive gland. In the pre-spawning phase, exposure for 7 days to NP significantly increased ALP levels in haemolymph from males exposed at all NP concentrations tested, whereas no significant variations were found in haemolymph from females. NP (0.05 and 0.1 mg/l) was also shown to increase ALP concentrations significantly in digestive gland of males, but not in those of females. Likewise, after 14 days’ exposure, ALP levels significantly increased in haemolymph from males only at 0.1 mg NP/l. Conversely, NP caused significant increases in ALP levels in digestive gland from both males (at all NP concentrations tested) and females (at 0.025 and 0.1 mg NP/l). These results demonstrate that NP induces Vg synthesis in C. glaucum. Interestingly, males were more responsive to NP than females.     

Polycyclic aromatic hydrocarbons in the coastal water,surface sediment and mullet Liza klunzingeri from northern part of Hormuz strait (Persian Gulf)

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in mullet (Liza klunzingeri), water and sediment from northern part of Hormuz strait (Persian Gulf). The concentration levels of total PAHs in L. klunzingeri, water and sediment were 133.99–268.57 ng g⁻¹ dry weight, 3.12–5.88 ng l⁻¹ and 42.29–228.9 ng g⁻¹ dry weight, respectively. Based on isomer ratios, analysis of the PAHs source in the sediment demonstrated that the PAHs come from pyrogenic and petrogenic origin. Risk assessment showed PAHs threshold concentrations to occasionally be exceeded in the study area.     

Potential use of dissolved cyanobacterial DNA for monitoring toxic Microcystis cyanobacteria in filtered water

Toxic and non-toxic Microcystis sp. are morphologically indistinguishable cyanobacteria that are increasingly posing health problems in fresh water systems by producing odours and/or toxins. Toxic Microcystis sp. produces toxicologically stable water soluble toxic compounds called microcystins (MCs) that have been associated with cases of aquatic life and wildlife poisoning and kills including some cases of human illnesses/deaths around the world. Thus, the need for rapid detection of toxic Microcystis sp. in surface water is imperatively a necessity for early mitigation purposes. Genomic DNA from potentially toxic Microcystis sp. comprises of ten microcystin synthetase (mcy) genes of which six major ones are directly involved in MCs biosynthesis. In Polymerase Chain Reaction (PCR) methodsmcy genes can be amplified from intracellular/extracellular genomic DNA using PCR primers. However, little is known about the limitations of sourcing genomic DNA templates from extracellular DNA dissolved in water. In this work, filtered water (0.45 μM) from a Microcystis infested Dam (South Africa) was re-filtered on 0.22 μM syringe filters followed by genomic DNA isolation and purification from micro-filtrates (9 mL). Six major mcy genes (mcyABCDEG) from the isolated DNA were amplified using newly designed as well as existing primers identified from literature. PCR products were separated by gel electrophoresis and visualized after staining with ethidium bromide. The limitation of using dissolved DNA for amplification of mcy genes was qualitatively studied by establishing the relationship between input DNA concentrations (10.0–0.001 ng/μL) and the formation of respective PCR products. The amplification of mcyA gene using new primers with as little as 0.001 ng/μL of DNA was possible. Other mcy gene sensitivities reached 0.1 ng/μL DNA dilution limits. These results demonstrated that with appropriately optimized PCR conditions the method can provide accurate cost-effective tools for rapid detection of toxic Microcystis sp. in water giving early information for water quality monitoring against MC producing cyanobacteria.