Occurrence and profiles of organic sun-blocking agents in surface waters and sediments in Japanese rivers and lakes

Sun-blocking agents including eight UV filters (UVF) and 10 UV light stabilizers (UVLS) were measured in water and sediment collected from 22 rivers, four sewage treatment plant effluents (STPE) and three lakes in Japan. Total sun blocking agents levels ranged from N.D. to 4928 ng/L and from 2.0 to 3422 μg/kg dry wt in surface water and in sediment, respectively. Benzyl salicylate, benzophenone-3, 2-ethyl hexyl-4-methoxycinnamte (EHMC) and octyl salicylate were dominant in surface water receiving wastewater effluents and STPE, although UV-328, benzophenone and EHMC were dominant in other surface water except background sites. Three UVF and nine UVLS were observed from all sediment and their compositions showed similar patterns with UV-328 and UV-234 as the most prevalent compounds. Homosalate, octocrylene, UV-326, UV-327, UV-328 and UV-234 were significantly correlated with Galaxolide^® in sediments. Concentrations of UV-327 and UV-328 also had strong correlation between those of UV-326 in sediment.     

Distribution and fate of organochlorine pesticide residues in sediments from the selected rivers in Taiwan

The contamination of organochlorine pesticides (OCPs) in sediments from selected rivers in Taiwan was investigated to evaluate the pollution potentials and hazard in river sediments. Da-han River and Erh-jen River were selected as the target rivers due to their serious pollution. A total of 40 surface sediment samples were collected at five sampling stations along the rivers. Results showed that the concentrations of various pesticides in sediments were in the range of 0.57-14.1 ng/g for sigmaHCH, 0.05-0.15 ng/g for aldrin, 0.12-5.8 ng/g for dieldrin, 0.22-0.64 for endrin, 0.24-6.37 ng/g for endosulfan and 0.21-8.81 ng/g for EDDT (p,p'-DDD, p,p'-DDE, p,p'-DDT). Among the OCPs, sigmaHCH, endosulfan and sigmaDDT were the most dominant compounds in the river sediments. Endosulfan sulfate was the most frequent detected compound in the sediments from the selected rivers. Also, sigmaDDT, dieldrin and beta-HCH were in abundance. Different contamination patterns between the selected river sediments were also observed. Da-han River was mainly contaminated with endosulfan sulfate and sigmaDDT. Whereas the main pesticides in Erh-jen River were beta-HCH and sigmaDDT. Among the cyclodiene compounds, dieldrin was in abundance in most of the sediments. Moreover, the frequencies of detection of the metabolites were higher than those of parent compounds, depicting that the sediments have contaminated for a long time. The results obtained in this study showed that there still exist a variety of OCP residues in the river sediments in Taiwan.     

Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua

The hydrographic basin of the Atoya river, located in the Department of Chinandega, one of the main cotton producing regions in Nicaragua, is intensively contaminated by pesticides. Samples of river waters and sediments, as well as strategically selected wells have been analyzed to study variations in the concentrations of organochlorine and organophosphorus pesticide residues between the dry season (November-April) and the rainy season (May-June). Generally, higher concentrations of pesticides have been detected in the river waters and sediments in the dry season. DDT, DDD, DDE compounds and toxaphene are the most frequent organochlorine residues found in the water and sediment samples, while endrin, aldrin, dieldrin and lindane are mainly found in the waters of rivers and wells. Organophosphorus compounds were rarely detected. However, residues of ethion, methyl-parathion and ethyl-parathion were found in high concentrations in some river and well water samples. Generally, organochlorine compounds tend to accumulate in the fine grain-size fractions, rich in organic matter, except DDE, which concentrates basically in the coarse grain-size fractions.     

Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River, Hai River and Liao River in northern China

The occurrence of four classes of 17 commonly used antibiotics (including fluoroquinolones, tetracycline, sulfonamides, and macrolides) was investigated in the sediments of the Yellow River, Hai River and Liao River in northern China by using rapid resolution liquid chromatography-tandem mass spectrometry. Higher concentrations were detected for most antibiotics in the sediments of the Hai River than in the sediments of the other rivers. Norfloxacin, ofloxacin, ciprofloxacin and oxytetracycline in the three rivers were most frequently detected with concentrations up to 5770, 1290, 653 and 652 ng/g, respectively. High frequencies and concentrations of the detected antibiotics were often found in the downstream of large cities and areas influenced by feedlot and fish ponds. Good fitted linear regression equations between antibiotic concentration and sediment physicochemical properties (TOC, texture and pH) were also found, indicating that sediment properties are important factors influencing the distribution of antibiotics in the sediment of rivers.     

Oil residues in Baltic sediment,mussel and fish. II. Study of the Finnish Archipelago 1979–1981

Aliphatic hydrocarbons and non-polar aromatic compounds have been analyzed after a spill of grude oil at Baltic Sea 1979 from drifting weathered oil glumps, sediment and sediment trap samples and bivalves at five areas of the Finnish Archipelago Sea. $\text{Mytilus}$ and flounder muscles and flounder livers were analyzed 1980 and 1981 from three of the previous five areas. The glumps were shown to be weathered grude oil. Sediment trap samples on the visibly contaminated area contained higher amounts of oil residues and in different ratios than the bottom sediments at the same areas. Extra local aliphatic hydrocarbon pollution was detected from the sediment traps at the reference area. Bivalves contained high amount of oil residues at visibly polluted but in some visibly non-polluted areas also 1979. Any significant decontamination was not detected at summer 1979 but next year the $\text{Mytilus}$ samples contained only traces if any and 1981 no detectable levels of aromatic oil residues. Aliphatic hydrocarbon residues in flounders showed no regional differences and no significant change of levels between 1980 and 1981. In contrary, the aromatic oil residues decreased to the non-detectable level in flounder muscles and to a significantly lower level in flouder livers 1981 related to 1980. Linear correlations of the analysis results are discussed.     

Chlorinated pesticide residues in surface sediments from the River Kaveri, south India

Chlorinated compounds have preferential attraction for organic phases found in sediments. Usage of chlorinated pesticides in agriculture and vector control is more in developing countries. The residue levels of HCH isomers, and DDT, and its metabolites were quantified in surface sediments from the River kaveri and Coleroon in Tamil Nadu state, South India. The concentration of HCH ranged from 4.35 to 158.4 ng g-1 (dry wt.). Among the isomers of HCH, alpha-HCH is predominant followed by beta and gamma-HCH. The levels of DDT varied from 0.69 to 4.85 ng g-1 (dry wt.). Among the DDT compounds, p,p'-DDE quantified more (> 40%) in all the sites. This suggests that p,p'-DDE is a major breakdown (dehydrochlorination) product of DDT in the sediment compartment. Higher concentration of HCH residues reveals its large usage in agriculture. The flux of pesticide residues from land to river including downward flux to sediment is less.     

Distribution of alkylphenols in the Pearl River Delta and adjacent northern South China Sea, China

The occurrence of alkylphenols (APs) was investigated in surface water and sediments from the Pearl River Delta and adjacent northern South China Sea. Most of the water samples contained detectable amounts of APs, ranging up to 0.628 microg l(-1) for nonylphenol (NP) and 0.068 microg l(-1) for octylphenol (OP). APs were found in all of the sediment samples with concentrations ranging from 59 to 7808 microg kg(-1) for NP and from 1 to 93 microg kg(-1) for OP. The Zhujiang River showed the highest concentrations of APs in both water and sediments. Significant decrease of APs concentrations going from the Zhujiang River to the Shiziyang River was observed. The Xijiang River contained concentrations of APs slightly higher in water but relatively lower in sediments than the Lingding Bay, which might be attributed to their different hydrodynamic and sedimentary characteristics. There was a decreasing trend of APs in water from the rivers to the estuary and further to the sea on the whole. In the Lingding Bay and its outer waters, concentrations of APs in sediments increased to a maximum and then decrease seaward, which was consistent with the distribution trend of the sediment organic carbon contents. Linear regression analyses showed the concentrations of APs were markedly correlated with the sediment organic carbon contents, indicating that the sediment organic carbon is an important factor controlling the levels of APs in sediments.     

Concentration and fate of persistent organochlorine pesticides in estuarine sediments using headspace solid-phase microextraction

The concentration and fate of persistent organochlorine pesticides (OCPs) in estuarine surface sediments in Erh-jen and Lan-yang rivers, Taiwan were investigated using headspace solid-phase microextraction (HSSPME) method to evaluate the possible pollution potential and guideline for OCP concentrations in Taiwan. The HSSPME method exhibits a good analytical performance with low detection limits for OCP determination in sediment. In addition, results obtained using the developed HSSPME method were in good agreement with those obtained using Soxhlet extraction in a certified sample. The developed analytical method was further applied to the determination of concentrations of OCP residues in surface sediments from the estuaries of the selected rivers in Taiwan. A total of 20 surface sediments from each river was collected from 10 sampling stations. The total OCP concentrations in sediments from Erh-jen River ranged from 0.17 to 5.04 ng/g-dw with the mean values of 0.25–1.24 ng/g-dw for HCHs, 0.10–0.89 ng/g-dw for cyclodienes and 0.16–0.64 ng/g-dw for DDTs. The concentrations of OCPs in sediments from Lan-yang River were in the range 0.37–0.9 ng/g-dw with an average of lower than 0.5 ng/g-dw. HCHs and DDTs were abundant in the estuarine sediments from the selected rivers. Results obtained in this study show that the origin of OCPs in the surface sediments from Erh-jen River is a combination of erosion of the weathered soils and long-range atmospheric transport, while the OCP concentrations found in Lan-yang River could be regarded as the background levels of OCPs in Taiwan.     

Current status and historical variations of phthalate ester (PAE) contamination in the sediments from a large Chinese lake (Lake Chaohu)

The residual levels of phthalate esters (PAEs) in the surface and two core sediments from Lake Chaohu were measured with a gas chromatograph–mass spectrometer (GC–MS). The temporal–spatial distributions, compositions of PAEs, and their effecting factors were investigated. The results indicated that di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), and di(2-ethylhexyl) phthalate (DEHP) were three dominant PAE components in both the surface and core sediments. The residual level of total detected PAEs (∑PAEs) in the surface sediments (2.146?±?2.255 μg/g dw) was lower than that in the western core sediments (10.615?±?9.733 μg/g) and in the eastern core sediments (5.109?±?4.741 μg/g). The average content of ∑PAEs in the surface sediments from the inflow rivers (4.128?±?1.738 μg/g dw) was an order of magnitude higher than those from the lake (0.323?±?0.093 μg/g dw), and there were similar PAE compositions between the lake and inflow rivers. This finding means that there were important effects of PAE input from the inflow rivers on the compositions and distributions of PAEs in the surface sediments. An increasing trend was found for the residual levels of ΣPAEs, DnBP, and DIBP from the bottom to the surface in both the western and eastern core sediments. Increasing PAE usage with the population growth, urbanization, and industrial and agricultural development in Lake Chaohu watershed would result in the increasing production of PAEs and their resulting presence in the sediments. The significant positive relationships were also found between the PAE contents and the percentage of sand particles, as well as TOC contents in the sediment cores.     

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.     

Polybrominated biphenyl ethers in marine fish, shellfish and river and marine sediments in Japan

The presence of polybrominated biphenyl ethers (PBBEs), commonly used as flame retardants, was confirmed in marine fish, shellfish and river and marine sediments in Japan. These compounds were detected in seven out of 17 marine fish and shellfish, though at low levels. Tetrabrominated biphenyl ether was a major component in marine organisms. However, sediment pollution by PBBEs, particularly that by decabrominated biphenyl ether, pose a serious problem in the rivers of Osaka but not in marine areas.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Petroleum hydrocarbon in surficial sediment from rivers and canals in Tianjin, China

Surficial sediment samples were collected from three rivers and six canals in Tianjin, China and analyzed for petroleum hydrocarbons. Chemical compositions and distribution patterns, as well as possible sources, of the petroleum hydrocarbons in the sediments were discussed. A series of petroleum hydrocarbons, including n-alkanes, isoprenoid alkanes, anteiso-alkanes, alkyl hexamethylene, hopanes and steranes were detected in the samples. The concentration of petroleum hydrocarbons varied in a wide range of 0.072-3.000 mg g(-1) in the surficial sediment of the rivers and canals in Tianjin. In the samples studied, the total concentrations of petroleum hydrocarbons in the sediment samples from North Canal, South Canal, and G3 segment of South Sewage Canal were higher than those from Hai River, South Sewage Canal and North Sewage Canal. Accumulation of pollutants in the sediments from reaches close to urban area was also observed. The PHC spatial variability is mostly affected by many local inputs. The main sources of petroleum hydrocarbons in the sediment in Tianjin were considered to be petroleum importation and biochemical degradation of organisms, including cuticular of aquatic vegetation and algae.     

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.     

PCDDs and PCDFs in sewage sludge, river and lake sediments from south west Germany

Sewage sludges and sediments of rivers and lakes are sinks for “persistent” organic compounds entering the environment. These matrices are therefore useful in the assessment of local and global pollution with certain compounds or classes of compounds. In recent years we have analyzed sediments of the rivers Neckar, Rhine, and Danube, from Lake Constance, and samples of sewage sludge from municipal waste water treatment plants of south-west Germany for PAH, phthalates, organochlorine pesticides, and PCBs. ¹ We have now analyzed a number of these samples for PCDDs and PCDFs. Isomer-specific analyses for 2,3,7,8-subsituted PCDDs/PCDFs were carried out in all cases.

In all samples PCDDs could be detected, and in most cases PCDFs as well. 2,3,7,8-TCDD was never detected at a detection limit of 0.01 ppb. In sediments (14 samples) the total PCDDs ranged from 0.1 to 2.9 ppb and PCDFs from “not detectable” to 1.2 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.06 ppb. In sewage sludges (15 samples) the total PCDDs ranged from 4 to 65 ppb and PCDFs from 1 to 7 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.57 ppb.

Comparison of PCDD/PCDF patterns of congeners and isomers for the sewage sludge and river sediment samples with those of stack gas emissions of waste incinerators and of pentachlorophenol allows the conclusion that the main source of PCDDs and PCDFs found in these samples is pentachlorophenol. Results of the Lake Constance sediment core indicate that here the atmospheric immission from waste incineration might be predominant.     

Organochlorine contaminants in the estuarine and coastal marine environments of the Fiji Islands

No information has been published on the presence of organochlorine pesticides and polychlorinated biphenyls in the Fiji Islands. This paper reports the first data on the concentration of a range of organochlorine compounds in sediments and shellfish in the estuarine and coastal marine environment around Fiji. Twenty-three sediment and two shellfish samples were analysed for 22 pesticides and related residues, and PCBs. While a significant number of organochlorines (20 pesticide related species and PCBs) was detected, the concentrations were generally very low (< 10 ng g), indicative of a relatively 'less contaminated' marine environment. Relatively high concentrations were observed only near the two major ports (Suva and Lautoka), with Suva harbour samples having the largest number of detectable species and the largest total concentrations of organochlorines (up to 91 ng g). No PCBs were detected in areas away from major industrial centres. The variations in the concentrations found, and the possible sources and movement of the organochlorine contaminants are discussed.     

Search for chlorobornanes in river sediments and in influents and effluents

In 1997, we collected nine river sediment samples, including one duplicate, from above and below three pulp and paper mills on the Wisconsin River in Wisconsin, USA, and one mill on Beaver Dam Creek in Ontario, Canada. We also obtained twenty split sediment samples from the Wisconsin River that were collected by the US EPA in collaboration with Indiana University. Finally, we collected influent and effluent samples from eight pulp and paper related industries in the US and Canada. We analyzed all sediment and water samples for hexa- through decachlorobornanes. We did not detect any chlorobornanes in most of the sediments. When chlorobornanes were detected, the concentration in sediments below pulp mills were similar to or less than in those from above the same mills. Chlorobornanes could not be detected in any of the influent or effluent samples. Thus, pulp and paper mills and relate facilities are not a source of chlorobornanes.     

Nitromusk compounds in San Francisco Bay sediments

Synthetic nitromusk fragrances are used in a wide variety of consumer products and can enter aquatic environments through wastewater effluent. Although nitromusks are known to be hydrophobic, little attention has been paid to their behavior in sediments. A sediment extraction method using sonication was developed and used to analyze samples from San Francisco Bay. Both musk xylene (MX) and musk ketone (MK) were found at low levels, with mean concentrations of 0.034 and 0.038ngg(-1), respectively. The highest concentrations were found in the southernmost region of the Bay. Samples were also analyzed from a nearby tidal channel fed by a wastewater treatment plant outfall. At this location both musk xylene and musk ketone were found at higher concentrations of 0.13-0.24ngg(-1) MX and 1.08-2.74ngg(-1) MK. A metabolite of musk xylene was also found at levels up to 4.08ngg(-1), suggesting that these metabolites may play an important role in the fate of nitromusk compounds. Concentrations of all three compounds were highest at the earliest of four sampling dates, and a geographic survey of sediments along the tidal channel showed that concentrations decreased rapidly with distance from the outfall and were close to background before the channel reached the Bay.     

Volatilization of contaminants from suspended sediment in a water column during dredging

Remedial dredging of contaminated bed sediments in rivers and lakes results in the suspension of sediment solids in the water column, which can potentially be a source for evaporation of hydrophobic organic compounds (HOCs) associated with the sediment solids. Laboratory experiments were conducted in an oscillating grid chamber to simulate the suspension of contaminated sediments and flux to air from the surface of the water column. A contaminated field sediment from Indiana Harbor Canal (IHC) and a laboratory-inoculated University Lake (UL) sediment, Baton Rouge, LA, were used in the experiments, where water and solids concentration and particle size distribution were measured in addition to contaminant fluxes to air. A transient model that takes into account contaminant desorption from sediment to water and evaporation from the water column was used to simulate water and sediment concentrations and air fluxes from the solids suspension. In experiments with both sediments, the total suspended solids (TSS) concentration and the average particle diameter of the suspended solids decreased with time. As expected, the evaporative losses were higher for compounds with higher vapor pressure and lower hydrophobicity. For the laboratory-inoculated sediment (UL), the water concentrations and air fluxes were high initially and decreased steadily implying that contaminant release to the water column from the suspended solids was rapid, followed by evaporative decay. For the field sediments (IHC), the fluxes and water concentrations increased initially and subsequently decreased steadily. This implied that the initial desorption to water was slow and that perhaps the presence of oil and grease and aging influenced the contaminant release. Comparison of the model and experimental data suggested that a realistic determination of the TSS concentration that can be input into the model was the most critical parameter for predicting air emission rates.     

Assessment of tin and butyltin species in estuarine superficial sediments from Gipuzkoa,Spain

Ten superficial sediments from river estuaries of Gipuzkoa (North Spain) were collected and analyzed for nine metals (including tin, Sn) and butyltin compounds (monobutyltin, MBT; dibutyltin, DBT; tributyltin, TBT). Total metal concentration in the fine fraction (<63 micrometer) of the sediment was determined in aqua regia--hydrofluoric acid extracts by atomic absorption spectrometry. The butyltin species (BTs) were firstly extracted from the sediments with hydrochloric acid-methanol mixture. After derivatization with sodium tetraethyl borate, the organotin compounds were extracted by solid phase microextraction (SPME) in headspace mode. A fiber coated with 100 micrometer poly(dimethylsiloxane) was used for SPME. The organotin species were analyzed by gas chromatography-flame ionization detection. Analysis of the certified reference sediment (PACS-2) shown the suitability of the procedures for determination of metal contents and DBT-TBT species in contaminated sediments. Factorial analysis was used to examine the main sources of metals. Three factors represented more than 89% of the total variance of the metal system, and the Sn was related with Cu-Zn-Pb suggesting the same pollution source. The BTs concentrations in the area were high (TBT ranged from 0.05 to 5.48 mg Sn kg(-1)). The percentage of total butyltin species ( summation operator BTs) respect to the total Sn amount was higher than 4% in all the sediments, showing in the Bidasoa river estuary a remarkable value higher than 20%. Hence, the studied estuarine sediments reflect a pollution that is related with historical industrial and fishing activities of the area.