A comparative study of mercury contamination in the Tagus estuary (Portugal) and major French estuaries (Gironde,Loire, Rhône)

Concentrations of mercury were determined for the waters, suspended matter and sediments of the Tagus and of major French estuaries.The Tagus estuary is one of the most contaminated by mercury derived from the outfalls of a chloralkali plant and from other industrial sources. In deposited sediments the median level, 1·0 μg Hg g^?1, is twenty times higher than the natural background and Hg contents depend on the sediment grain-size, age and the distance from waste-outfalls. Suspended matter is more regularly and highly contaminated (median value: 4·5 μg Hg g^?1). In the French estuaries Hg levels in the suspended material decrease with salinity due to dilution and/or remobilization processes. In June 1982, in the Loire estuary, high values of Hg are observed in the middle estuary and attributed to urban and industrial sources.In the Tagus estuary, the general distribution of total dissolved Hg confirms the contamination: it increases seaward from 10 ng 1^?1 in the river to 80 ng 1^?1 in the estuary outlet. The dissolved Hg is almost totally organic in the river, inorganic in the middle estuary due to inorganic Hg effluents and again organic in the lower estuary. This variation is related to the dissolved organic carbon values. The dissolved Hg levels in the Loire Estuary (5–300 ng 1^?1) are much higher than in the Gironde estuary (3–6 ng 1^?1) and of the same order as those observed in the Tagus estuary.     

Potential rates and environmental controls of denitrification and nitrous oxide production in a temperate urbanized estuary

Denitrification may play a major role in inorganic nitrogen removal from estuarine ecosystems, particularly in those subjected to increased nitrate and organic matter loads. The Douro estuary (NW Portugal) suffers from both problems: freshwater input of nitrate and organic load from untreated wastewater discharges. To assess how these factors might control sediment denitrification, a 12-month survey was designed. Denitrification potential and nitrous oxide (N₂O) production were measured at different locations using the slurry acetylene blockage technique. Denitrification rate ranged from 0.4 to 38 nmol N g⁻¹ h⁻¹, increasing towards the river mouth following an urban pollution gradient. N₂O production, a powerful greenhouse gas implicated on the destruction of the ozone layer, was significantly related with sediment organic matter and accounted for 0.5–47% of the N gases produced. Additional enrichment experiments were consistent with the results found in the environment, showing that sediments from the upper less urban stretch of the estuary, mostly sandy, respond positively to carbon and, inversely, in organic rich sediments from the lower estuary, the denitrification potential was limited by nitrate availability. The obtained results confirmed denitrification as an important process for the removal of nitrate in estuaries. The presence of wastewater discharges appears to stimulate nitrogen removal but also the production of N₂O, a powerful greenhouse gas, exacerbating the N₂O:N₂ ratio and thus should be controlled.     

Effects of organic pollutants on methanogenesis,sulfate reduction and carbon dioxide evolution in salt marsh sediments

Anaerobic salt marsh sediments were amended with a variety of organic pollutants and the effects on methanogenesis, sulfate reduction and carbon dioxide evolution were examined. Addition of 1000 μg g^?1 (dry weight sediment) Arochlor 1221, lindane, endrin, benzene and phenanthrene resulted in no significant effects on the activities studied. Methanogenesis was inhibited by 1000 μg g^?1toxaphene, PCP, chlordane, naphthalene, DDT, Kepone and heptachlor and by 100 μg g^?1 PCP and toxaphene. At 1000 μg g^?1 naphthalene and toxaphene and 100 μg g^?1 PCP, a period of initial inhibition of methanogenesis was followed by stimulation relative to controls. Arochlor 1254 (1000 μg g^?1) and Temik (500 and 10 μg g^?1) stimulated methanogenesis from the outset. Temik at 500 μg g^?1 gave the greatest stimulation of methanogenesis (900% of controls) of any of the compounds studied. Sulfate reduction was inhibited by 1000 μg g^?1 PCP, toxaphene, naphthalene and chlordane and by 500 μg g^?1 atrazine and 100 μg g^?1 heptachlor. Sustained inhibition of sulfate reduction by naphthalene, toxaphene and PCP may have contributed to the stimulation of methanogenesis. Carbon dioxide evolution was not significantly affected by most of the compounds studied except for 100 μg g^?1 PCP and 1000 μg g^?1 aphthalene, each of which gave significant inhibition in only one of three experiments.Concentrations of individual organic pollutants required to cause observable effects were high. It is concluded that, except for highly polluted sediments, methanogenesis, sulfate reduction and CO₂ evolution would not be affected by the compounds studied here at concentrations typically found in the environment.     

The widespread occurrence of highly branched acyclic C20, C25 and C30 hydrocarbons in recent sediments and biota—A review

The occurrence of widely distributed acyclic isoprenoid hydrocarbons (C_2O, C₂₅ and C₃₀) with highly branched structures, in sediments and biota is reviewed. The compounds occur as alkanes and alkenes with from one to at least four double bonds in young aquatic (both marine and lacustrine) sediments from many parts of the globe (e.g. Peru, Antarctica, Gulf of Suez, North Sea, Atlantic) sometimes in high concentrations (e.g. 40 μg g⁻¹ sediment) relative to other hydrocarbons. However, the compounds rapidly disappear in older sediments, possibly due to biodegradation and reaction with sedimentary sulphur. These and other factors are discussed.The sources of this fascinating group of hydrocarbons remain largely unknown, though evidence points to algae (possibly diatoms) as one possibility. The recent identification of related sulphur-containing compounds in a crude oil promises to extend the number of reports of these compounds still further, and to increase their importance as environmental biological markers.     

Distribution and sources of organochlorine pesticides in water and sediments from Daliao River estuary of Liaodong Bay,Bohai Sea (China)

The levels of 19 kinds of organochlorine pesticides (OCPs) in the aqueous phase, suspended particulate matter (SPM), pore water and sediments from Daliao River estuary of Liaodong Bay (Bohai Sea) in northeast China were investigated to evaluate their potential pollution risks. The total OCPs concentrations in the aqueous phase, SPM, pore water and sediments were 3.7–30.1 ng l⁻¹, 4.6–52.6 ng l⁻¹, 157–830 ng l⁻¹ and 2.1–21.3 ng g⁻¹ dry weight, respectively. The concentrations of OCPs, in the Daliao River estuary, are in the mid-range, as compared to those reported in other estuaries worldwide. The distribution of HCHs and DDTs were different indicating different contamination sources. Lindane is the main type of HCH and continuing use in northeast China of ‘pure’ HCH (lindane) rather than technical HCH accounts for the source. The ratios of (DDE + DDD)/DDT in the samples indicate no recent inputs of these chemicals to the estuary.     

Spatial Distribution of Polychlorinated Biphenyls （PCBs） Contaminants in the Tidal-flat Sediments of Yangtze Estuary

1 IntroductionYangtze River estuary is the biggest one in China, and there are domestic and manufactural rubbish disposal sites for Shanghai city in this tidal-flat. The Shanghai city, the whole Yangtze delta, or even all the Yangtze basin, will be PCBs contaminant sources of Yangtze estuary tidal-flat[1]. According to literatures so far, only two investigations for waters have included PCBs in the Yangtze estuary[2, 3]. No PCBs pollution of the tidal-flat sediments has been reported…     

Chemistry of sediments in relation to trophic condition of eight Rotorua Lakes

Abstract

Chemical parameters (pH, Eh, carbon, Kjeldahl nitrogen, total phosphorus, 0.5M H₂SO₄‐extractable phosphorus, organic phosphorus, and water‐soluble phosphorus) were measured in the surface layers of sediments collected from various depths in Lakes Rotowhero, Okaro, Ngapouri, Rotokakahi, Okareka, Tikitapu, Okataina, and. Rotoma during October 1972. The sediments of the productive geothermal lake, Rotowhero, were markedly different from those of the cold‐water lakes: they had relatively low pH values, high carbon (mean 8.5%) and organic phosphorus (mean 4160 μg.g^?1) concentrations, and very high total phosphorus concentrations (mean 4770 μg.g^?1), probably as a result of enrichment by hot springs.

The mean concentrations in the sediments of the cold‐water lakes were carbon 3.2–7.9%, Kjeldahl nitrogen 3380–8310 μg.g^?1 and phosphorus 690–1780 μg.g^?1. These concentrations are within the ranges for New Zealand terrestrial topsoils, but the lake sediments appear enriched in phosphorus relative to local topsoils. Total carbon, nitrogen, and phosphorus concentrations of sediments tended to be highest in the eutrophic lakes (Okaro, Ngapouri) although the deep oligotrophic lakes (Okataina, Rotoma) had relatively high total phosphorus concentrations (means 1400, 1510 μg.g^?1). Overall, the carbon, nitrogen, and phosphorus concentrations of the sediments showed little relationship to the trophic state of the lake.

Organic phosphorus concentrations of the surface layers of sediments were similar in all the cold‐water lakes (mean 319 μg.g^?1). The proportion of the total phosphorus apparently ‘fixed’ in mineral material was minimal (0–1%) in sediments from the eutrophic and mesotrophic lakes, but in the oligotrophic lakes was similar to that in New Zealand topsoils (9–14%). Reducing conditions may cause solution of a high proportion of the ‘fixed’ phosphorus in the eutrophic lakes.

The water‐soluble phosphorus concentrations in the sediments of the five shallow cold‐water lakes (Okaro, Ngapouri, Rotokakahi, Okareka, Tikitapu) correlated positively with trophic state and with concentrations of dissolved phosphorus in the lake waters.

Carbon, nitrogen, and phosphorus concentrations in the sediments tended to vary with overlying water depth. This should be considered when comparisons are made between lakes.     

Enteroviruses in mussels and marine sediments and depuration of naturally accumulated viruses by green lipped mussels (Perna canaliculus)

Surveys were carried out over 16 months to assess the distribution of enteroviruses of human origin in sediments and mussels near two sewage outfalls on the North Taranaki Coast, New Zealand. Enteroviruses were present in high numbers in both sediments and shellfish near the New Plymouth sewage outfall with maximum virus levels of 32 000 pfu 100 g^‐1 of wet mussel tissue and 59 pfu 100 g^‐1 of wet sediment material. Viruses were recovered occasionally from sediments and mussels near the Waitara Borough outfall. Coxsackievirus B4 was the predominant virus type isolated but CB5 and Poliovirus types 1, 2, and 3 were also recovered. Attempts to depurate virus‐contaminated New Plymouth mussels, by keeping them in water for 8 days with daily water replacement, did not achieve a significant reduction in virus numbers.     

Apports de nutriments et développement phytoplanctonique en baie de Seine

As part of the Programme National d'Océanographie Côtière, the nutrient dynamics of the Bay of Seine were studied between 1992 and 1994 in order to complement work on ecological modelling. Firstly, the River Seine's nutrient fluxes were established: 80 000–130 000 t a⁻¹ of dissolved inorganic nitrogen, 6 400–8 4001 a⁻¹ of dissolved phosphorus and 20 000–77 000 t a⁻¹ of dissolved silicium. Estuarine processes were taken into account. Consequences of nutrient loading for the bay were then evaluated at the pelagic level (nutrient and chlorophyll enrichments) and the benthic level (distribution of various phosphorus fractions in superficial sediments). The large continental inputs always induce concentration gradients in the water from the mouth of the river to the northwest of the bay. The northward spreading of fine particulate matter controls the distribution of adsorbed phosphate and iron-aluminium bound phosphate in sediments. In contrast, calcium bound phosphate, the main fraction in sediments, is not affected by river inputs. Organic phosphorus in sediments is related to phytoplankton blooms, with increasing concentrations during productive periods; afterwards the fast recycling prevents sedimentary accumulation. The nutrient depletions observed beyond the turbid plume during spring 1992 enabled the calculation of nutrient uptake rates, and the comparison of these rates with phytoplankton biomass (chlorophyll a + phaeopigments). Ratios of nutrient consumption to pigment concentration were estimated at 1 μmol μg⁻¹ for nitrogen, 0.05 for phosphorus and 0.5 for silicate. These values, as N/P and Si/N uptake ratios (respectively 17.5 and 0.4), were similar to usual values.     

Fatty acid composition of surface sediments in the subtropical Pearl River estuary and adjacent shelf,Southern China

Surface sediments (10 cm) of the subtropical Pearl River estuary and adjacent shelf, Southern China were collected. Fatty acids and compound-specific carbon isotopic analyses were determined to infer their sources and biogeochemical cycle of this lipid in the subtropical Pearl River estuary and adjacent northern South China Sea (SCS). The total concentrations of fatty acids ranged from ∼1.28 to ∼42.25 μg g⁻¹ dry weight. The levels of polyunsaturated fatty acids (PUFA) were low (0.2–4.8% of total fatty acids), suggesting that fatty acids derived from algae were effectively recycled during the whole settling and depositing process. Bacterial fatty acids were significantly high and terrigenous fatty acids were low in the sediments. Principal component analysis (PCA) of the data also indicates that a clear separation of the biogeochemical sources can be seen. The δ¹³C values of bacterial fatty acids, i.e., i/aiC₁₅ (−22.9‰ to −29.4‰) suggest that bacteria within the sediments mainly utilize a labile pool of organic matter derived from algae for their growth in the subtropical Pearl River estuary system.     

Mass balance of lead through a small macrotidal estuary: The Morlaix River estuary (Brittany,France)

Dissolved and particulate lead were measured over an annual cycle (12 surveys between February 1998 and January 1999) in the Morlaix River estuary (Brittany, France). The concentrations were investigated in both the water column and the sediment of the river bottom in relation to hydrological conditions. In the water column, dissolved and particulate lead concentrations ranged from 0.1 to 4.4 nM and from 0.04 to 1.9 μmol g^− 1, respectively. Lead concentrations in surface sediment varied from 0.04 to 0.19 μmol g^− 1 and concentrations in the sediment pore water of the estuary were below the detection limit. Compared with the ranges known for pristine estuaries, concentrations of Pb in the water column of the Morlaix River estuary were found to be much higher. Concentrations of Pb also exceeded the lower range of those known for industrialized estuaries. Extensive agricultural activities in the drainage basin may be responsible for Pb levels above pristine conditions. Furthermore, the sediment appeared not to be contaminated. A mass balance was constructed quantifying all known sources and sinks for the Pb in the estuary. Riverine input accounts for most of the total annual metal flux. Burial in sediments was the major sink within the estuary, which acts as a trap especially for the particulate lead. The mass balance shows that the metal accumulation ranged between 414.6 and 446.0 kg year^− 1.     

Trace metals and hydrocarbons in sediments from the Southampton water region,with particular reference to the influence of oil refinery effluent

The concentrations of a number of trace metals (Co, Ni, Cu, Zn, Ag, Cd and Hg) have been determined in sediments from cores collected in the Southampton Water region. Measurements of total hydrocarbons were also made on several of the cores. Markedly elevated concentrations of copper, up to 362 μg/g dry wt, were found in sediments which were collected close to the discharge points of oil refinery outfalls and which also showed concentrations of total hydrocarbons considerably greater than the background levels for the estuary. The results of selective chemical extractions showed that much of the copper was present in the non-lattice fraction of the sediment. Although the concentrations of Co, Ni, Zn and Cd were significantly correlated with those of copper in the core showing the highest concentrations of this element, these metals were not enhanced in comparison with the levels found in several other parts of the estuary. Variations in concentrations of metals in sediments throughout the estuary were not correlated with differences in organic carbon content.     

Mercury in the Southern North Sea and Scheldt estuary

Dissolved and particulate mercury and methylmercury concentrations were determined in the Southern Bight of the North Sea and the Scheldt estuary in the period 1991–1999. Mercury and methylmercury concentrations are higher before 1995 than after 1995, especially in the fluvial part.The North Sea: In the offshore stations, dissolved Hg concentrations are generally higher in winter than in summer while the reverse is true for particulate Hg K_D values (K_D=the concentration of particulate Hg (Hg_P in pmol kg⁻¹) divided by the concentration of dissolved Hg (Hg_D in pmol l⁻¹)) range from 100,000 to 1000,000 l kg⁻¹. Dissolved methylmercury concentrations vary from 0.05 to 0.25 pmol l⁻¹ in summer and from d.l. to 0.23 pmol l⁻¹ in winter and particulate methylmercury concentrations from 1.8 to 36 pmol g⁻¹ in summer and from 0.9 to 21 pmol g⁻¹ in winter. The K_D ranges from 9,000 to 219,000 l kg⁻¹.The Scheldt estuary: In winter, dissolved Hg concentrations are elevated in the upper estuary, decrease exponentially in the low salinity range followed by a very slow decrease towards the mouth. In summer, they are low in the fluvial part, increase in the low salinity range or in the mid-estuary and sometimes show an increase in the lower estuary. Particulate Hg concentrations do not show any seasonal trend.Dissolved MMHg concentrations are much lower in winter, when maximum concentrations are found in the upper estuary, than in summer. In summer, the MMHg concentrations are low at low salinity, they show a first increase in the salinity range from 3 to 12, a decrease in the mid-estuary and a second increase in the lower estuary.The highest particulate MMHg concentrations are found in the upper estuary, while in the lower estuary generally lower and more constant values are observed. The ratio of dissolved MMHg to dissolved Hg (cruise averages between 1.3% and 20%), is higher than the ratio of particulate MMHg to particulate Hg (cruise averages of 0.27–0.90%). The K_D values for MMHg are lower in the summer (30,000–65,000) than in autumn and winter (77,000–114,000).The Scheldt river: In the fluvial part of the Scheldt, dissolved increases in the most upstream stations, while particulate Hg shows no particular pattern. Dissolved MMHg ranges from 0.1 to 0.39 pmol l⁻¹ and particulate MMHg from 3.1 to 43.5 pmol g⁻¹. The MMHg concentrations are comparable to those found in the estuary and no seasonal variations could be observed.     

Copper,chromium, and lead in Manukau Harbour sediments

A limited survey was undertaken to determine the concentrations of copper, lead, and chromium in sediments of the upper Manukau Harbour, New Zealand. The concentrations of copper and chromium (33–70 and 70–107 μg g^‐1 respectively) were of the same order of magnitude as those reported for other New Zealand harbours. However, lead concentrations (98–247 μg g^‐1) were higher than those found for the other harbours. This may be a consequence of higher traffic densities in the surrounding area.     

长江口及毗邻海区沉积物中磷的分布特征

于2006年6月和2007年4月在长江口及毗邻海区采集了表层沉积物样品,利用水淘选法对沉积物进行了粒径分级,并采用改进后的SEDEX方法对沉积物样品及分粒级沉积物样品进行了磷形态分析。结果表明,2006年6月和2007年4月长江口及毗邻海区沉积物总磷变化分别为12.56~19.64μmol/g和8.99~19.91μmol/g,其中碎屑磷是磷的主要存在形态。可交换态磷、铁结合态磷、有机磷、自生磷灰石磷及难分解有机磷在长江口外的平面分布比较一致,均在紧邻长江口门外、杭州湾外的条状带出现了含量的高值,而在口门内及口门外河口靠海一侧碎屑磷含量较高。不同形态磷在不同粒径沉积物中的含量不尽相同:有机磷、自生磷灰石磷以及难分解有机磷是小于8μm粒级沉积物中磷的主要组成部分,而且其在总磷中所占比例随沉积物粒径的增加而下降;碎屑磷则主要集中在粗沉积物中,为32~63μm及大于63μm粒级沉积物中磷的主要贡献者。沉积物的粒度分异以及各形态磷在不同粒径沉积物中含量的差异,共同影响着河口沉积物中磷的分布。     

Nereis diversicolor: an Unreliable Biomonitor of Metal Contamination in the 'Ría de Bilbao' (Spain)

Abstract. Samples of the polychaete Nereis diversicolor O.F. M üller and surficial sediments from a clean and a polluted estuary were taken during a year at monthly intervals to determine, by comparison, the range of temporal fluctuations in trace metal concentrations. Whereas metal variations in surficial sediments were more pronounced in the polluted estuary, concentrations in N. diversicolor in both estuaries showed a wide range of temporal variation that surpassed that of surficial sediments. A clear decline in all metals studied (except Mn) from polluted sediments was noted after episodes of strong rainfall. In the reference estuary the fluctuations were less pronounced. Metal body burdens in N. diversicolor from the two estuaries were usually quite similar even though total levels in sediments differed considerably, indicating a lack of worm-sediment relationship. The low level of Cu, Cr and Pb in the tissues of N. diversicolor suggest a mechanism which prevents the polychaete from being exposed to these metals in highly polluted sediments. Therefore, it is concluded that N. diversicolor cannot be considered to be an ideal biomonitor of metal contamination in the polluted Bilbao Estuary.     

Behaviour of arsenic on the continental shelf off the Gironde estuary: Role of phytoplankton in vertical fluxes during spring bloom conditions

The arsenic (As) cycle in the marine environment is known to be sensitive to biological activity. Within the scope of the National Coastal Oceanography Program, we undertook a specific study of the behaviour of this element in a water column on the continental shelf of the Bay of Biscay off the Gironde estuary during two oceanographic cruises conducted in May 1994 and May 1995. Various chemical forms were measured: arsenate (As3), arsenate (As5), monomethylarsenic (MMA), dimethylarsenic (DMA) and dissolved total As after ultraviolet mineralization. The net flux of total As from the Gironde estuary was evaluated as well as its effect on the concentration in surface marine waters. The vertical profiles in the coastal zone during a period of active primary production confirmed a certain analogy between arsenates and phosphates as well as the formation of As3 and DMA. The importance of organoarsenic species not directly accessible to the formation of volatile hydrides is demonstrated. Their presence modifies assessments, reducing the deficit of dissolved total As in the euphotic layer to just 5%. For particles, the As content in phytoplankton was estimated at 6 μg·g⁻¹ compared to 20 to 30 μg·g⁻¹ in iron- and aluminium-rich terrigenous particles. These results do not invalidate the role of phytoplankton in the speciation of dissolved As but indicate that their involvement in vertical transfers was apparently not predominant in the zone under study.     

Contrasting food-web support bases for adjoining river-influenced and non-river influenced continental shelf ecosystems

Nutrient and chlorophyll a concentrations and distributions in two adjoining regions of the South Atlantic Bight (SAB), Onslow Bay and nearshore Long Bay, were investigated over a 3-year period. Onslow Bay represents the northernmost region of the SAB, and receives very limited riverine influx. In contrast, Long Bay, just to the south, receives discharge from the Cape Fear River, draining the largest watershed within the State of North Carolina, USA. Northern Long Bay is a continental shelf ecosystem that has a nearshore area dominated by nutrient, turbidity and water-color loading from inputs from the river's plume. Average planktonic chlorophyll a concentrations ranged from 4.2 μg l⁻¹ near the estuary mouth, to 3.1 μg l⁻¹ 7 km offshore in the plume's influence, to 1.9 μg l⁻¹ at a non-plume station 7 km offshore to the northeast. Average areal planktonic chlorophyll a was approximately 3X that of benthic chlorophyll a at plume-influenced stations in Long Bay. In contrast, planktonic chlorophyll a concentrations in Onslow Bay were normally <0.50 μg l⁻¹ at a nearshore (8 km) site, and <0.15 μg l⁻¹ at sites located 45 and 100 km offshore. However, high water clarity (K_PAR 0.10–0.25 m⁻¹) provides a favorable environment for benthic microalgae, which were abundant both nearshore (average 58.3 mg m⁻²) and to at least 45 km offshore in Onslow Bay (average 70.0 mg m⁻²) versus average concentrations of 10–12 mg m⁻² for river-influenced areas of Long Bay. This provides evidence that much of the inner shelf food web in Onslow Bay is based on benthic microalgal production, in contrast to a plankton-based food web in northern Long Bay and more southerly areas of the SAB.     

The behavior of iron,manganese and silicon in the Peconic River estuary,New York

The behavior of dissolved and particulate iron and manganese and dissolved silicon has been studied as a function of chlorinity in the Peconic River estuary, New York. This study sought to identify important geochemical processes in a relatively pristine estuary facing increasing anthropogenic impact.Dissolved iron behaved in the classical non-conservative manner exhibiting removal of nearly 80% at very low chlorinities, while particulate iron increased by a corresponding amount over the same chlorinity range. Dissolved manganese was enriched by up to 200% over its predicted concentration at low and intermediate chlorinities by desorption from suspended particulates and by a probable benthic flux. Dissolved silicon was enriched by up to 100% at low and intermediate chlorinities also from a probable benthic flux. These fluxes were estimated to be 5 μg cm^?2 day^?1 for dissolved manganese and 70 μg cm^?2 day^?1 for dissolved silicon.The quantity of both particulate iron and manganese increased at high chlorinities due to an influx of suspended inorganic particulates. In the intermediate to high chlorinity region, oxidation of sediment-derived manganese is believed to contribute to the observed increase in particulate manganese.Total iron was essentially conservative throughout most of the estuary, while total manganese was non-conservative presumably due to extensive remobilization of dissolved manganese from the sediments.     

Fate modeling of nonylphenol ethoxylates and their metabolites in the Dutch Scheldt and Rhine estuaries: validation with new field data

The environmental behavior of nonylphenol ethoxylates (A₉PEO) in the Rhine and Scheldt estuaries (The Netherlands) was investigated using a hydrodynamic advection-dispersion fate model (ECoS 3). The model was validated with the results of field studies, in which A₉PEO as well as the metabolites nonylphenoxy ethoxy acetic acids (A₉PEC) and nonylphenol (NP) were analyzed in sediment, water and suspended particulate material (SPM) samples using LC–MS methods. Maximum actual concentrations observed in surface sediments were 620, 560 and 1100 ng g⁻¹ d.w. for A₉PEO, A₉PEC and NP, respectively. In the dissolved phase, maximum observed concentrations amounted to 1100 ng L⁻¹ (A₉PEO), 6500 ng L⁻¹ (A₉PEC) and 960 ng L⁻¹ (NP). Clear spatial trends were observed for dissolved A₉PEO and metabolites in the Scheldt estuary, with decreasing concentrations going downstream. This concentration decrease was steeper than for conservatively behaving compounds. This trend was not visible in the Rhine estuary. The fate model was applied to A₉PEO and metabolites in both estuaries. Transport of chemicals in the water column was considered as a longitudinal one-dimensional process through a number of estuary segments. For the Rhine estuary, to cope with the stratification observed, a model structure was chosen consisting of two water layers above each other, between which exchange was possible. Sedimentation/erosion processes were included in the model. A biodegradation scheme was incorporated, and rates were adjusted to fit the calculated concentration profiles with the actual profiles of both A₉PEO and its metabolites. In this way, field biodegradation rates for A₉PEO, A₉PEC and NP could be derived, which were in agreement with values from literature. The measured dissolved concentration profiles as well as salinity and concentrations of SPM could be described successfully by the model. The concentrations calculated in SPM and sediment were of the same order of magnitude as the actual concentrations. In the Rhine estuary, additional sources of A₉PEO had to be included to account for the relatively high concentrations in the middle of the estuary. The fate model for the Scheldt estuary could be slightly improved by using salinity-dependent biodegradation rates. A sensitivity analysis of the model showed that in the Scheldt estuary, the environmental process with the strongest influence on the dissolved concentration profiles of A₉PEO and metabolites is biodegradation. In the Rhine estuary, the water residence time is too short for significant biodegradation to occur, and in this estuary the dissolved concentration profiles were mainly influenced by the additional A₉PEO sources.