Intensifying groundwater acidification at Birkenes, southern Norway

Groundwater chemical data from Birkenes, southern Norway, collected during the period October 1980 to November 1993, reveal intensifying acidification in the 1990s, as evidenced by decreases in pH, acid-neutralising capacity and alkalinity, and increases in hardness/alkalinity ratio, ‘acidification’, nitrate, non-marine sulphate (SO₄^*), non-marine hardness (Ca^* + Mg^*) and dissolved aluminium. The whole monitoring period is characterised by slopes of four or more on a plot of (Ca^* + Mg^*) vs. alkalinity.

Owing to its proximity to the sea, the Birkenes catchment receives seasalt-influenced precipitation, which results in episodic, natural acidification of the groundwater via cation exchange of marine Na⁺ with soil-bound H⁺ and/or Al³⁺. However, it is uncertain whether all of the recent groundwater acidification can be attributed to intensifying seasalt deposition alone: the steep slopes on the (Ca^* + Mg^*) vs. alkalinity plot and the increase in groundwater SO₄^* suggest that strong acids, of possible anthropogenic origin, may be involved. Additionally, seasalt deposition appears not to have increased during the 1990s: Cl⁻ content in precipitation has not increased significantly and river water pH has not decreased significantly over the period 1990–1993. The suggestion is made that the observed intensification in groundwater acidification at Birkenes partly results from the exhaustion or weakening of an acid buffering system caused by soil acidification, under persisting, even if abating, anthropogenic acid loading.     

Contrasts in storm event hydrochemistry in an acidic afforested catchment in upland Wales

The hydrochemistry of stream water in an acidic afforested catchment in the Welsh uplands was monitored routinely between 1985 and 1990. Nineteen storm episodes were sampled intensively during this period. Although the general storm response of the stream can be characterised by increased concentrations of H⁺, Al and dissolved organic carbon (DOC), and a dilution of Ca and SiO₂, the detailed hydrochemistry of individual acid episodes exhibited marked contrasts. The minimum pH reached during specific episodes ranged from 4.1 to 5.0, and peak dissolved Al concentrations varied from 9 to 44 μmol l⁻¹. The reasons for such differences in the hydrochemical response can be identified for each individual episode by examining the complex interactions between (1) the quantity and quality of event precipitation, (2) antecedent patterns of weather and atmospheric deposition and (3) the hydrological processes which dominate the storm runoff response. The dynamic nature of catchment hydrology was found to exert a particularly strong influence on the hydrochemistry of specific acid episodes.     

The effects of a pelletised limestone treatment on drainage water acidity within a forest catchment in mid-Wales

Three headwater source areas were identified within a strongly acidified forest catchment in the Llyn Brianne area of central Wales. Each received an aerial application of between 10 and 16 t ha⁻¹ of limestone pellets (composed of powdered chalk, starch and bentonite) in November 1988. The pH, calcium and aluminium levels within soil water and stream water were assessed at fortnightly intervals over a 3 year period to determine the impact of the treatment on drainage water acidity. The results demonstrated the importance of identifying the effective source areas within a catchment and treating these with a readily available form of powdered limestone. Treatment with a pelletised form was unsuccessful in eliminating periods of low pH and high aluminium concentrations within the headwaters of the forested catchment. This was attributed to the slow breakdown and dissolution of the limestone pellets under the forest canopy and the reduced importance of the surface runoff pathways owing to pre-afforestation cultivation and drainage, and soil drying by the forest crop.     

Correlation of magnetic properties with Δ(Sr) of igneous rocks from the northeast Pacific and Gulf of California

The magnetic properties of basalts and diabases recovered under Legs 63 and 64 of the Deep Sea Drilling Project are summarized. They are first correlated with the measured grain sizes of the opaque minerals and the overall alteration states of the rocks, the latter measured by conventional chemical parameters such as water content, total volatiles content, and Fe₂O₃/FeO ratio. It is shown, however, that the decrease in ⁸⁷Sr/⁸⁶Sr upon leaching (Δ(^87/86Sr)) is perhaps the best quantifier of the overall alteration state of the whole rocks as well as of the degree of low-temperature oxidation suffered by the titanomagnetites. It is well correlated with Curie-point variations caused by changes in the Fe³⁺/Fe²⁺ ratio.     

甘肃东南地区温泉流体地球化学特征

根据氢、 氧、 氦同位素与水化学组分资料, 讨论了甘肃东南地区温泉水的来源、 地球化学变化及其与2008年汶川M_S8.0地震的关系。 测定结果表明: 样品的溶解性固体总量(TDS)范围为241.7~2 372.1 mg/L。 采集的7处温泉(通渭汤池河温泉、 清水地震台、 天水地震台、 武山地震台、 武山22号井、 成县地震台、 武都地震台)水样可归为四种化学类型: Na·Ca-SO₄、 Ca·Mg-SO₄、 Na-HCO₃·SO₄、 Ca·Mg-SO₄·HCO₃。 地下热水的化学类型与裂隙深度和围岩的岩性有关, 离子浓度和断裂深度基本成正相关。 通渭汤池河温泉和武都地震台的δ18O和δD值分别在-11.4‰ ~ -7.6‰和-85.7‰ ~ -57.1‰的范围内, 通渭汤池河温泉和武都地震台中³He/⁴He的值分别为0.4×10^-7和12.7×10^-7。 氢、 氧、 氦同位素组成特征表明温泉水源于大气降水, 在循环过程中经历了水岩反应, 且可能有地表水的混入。 2008年汶川M_S8.0地震发生后, 研究区域内温泉水中K⁺、 Ca²⁺含量总体上升, SO^2-₄、 Cl^-含量总体下降, Na⁺含量变化不明显; 热水循环深度受地震影响发生变化。 本文确定了甘肃东南地区温泉来源、 水化学类型成因及其与汶川M_S8.0地震的关系。     

Enrichment by inorganic nutrients and oxygen utilization rates in Elefsis Bay (1973–1976)

This paper concerns the enrichment by nutrients and the oxygen utilization rates of an intermittently anoxic basin. The concentration of nutrients and dissolved oxygen have been determined during seasonal surveys of water characteristics. The oxygen utilization rates ranged between 1.3 and 1.8 ml l.⁻¹ month⁻¹ from March to June and were considerably higher than those reported for oceanic waters. The nutrients enrichment appears to be considerably influenced by eutrophication and human activity. During anoxic conditions in summer, the mineralization of organic matter was associated with consequent accumulation of enormous amounts of nitrogen (ammonia), phosphates and silicates. Nutrient ratios underwent great fluctuation mainly due to anoxic conditions.     

河套盆地周缘泉水化学组分对2015年4月15日阿左旗MS5.8地震的响应*

根据河套盆地周缘断裂带泉水的氢、氧同位素组成和水化学组分,讨论了该区地下水的化学类型、成因及其与地震活动的关系。于2014年9月下旬和2015年4月15日M_S5.8阿左旗地震震后在河套盆地周缘的乌拉山断裂带、色尔腾断裂带、狼山断裂带以及桌子山断裂带采集了17个泉水和井水样品,测得水样的TDS分布在143.8~42 553.0mg/L范围内,δD和δ¹⁸O值分别在-83.6‰~66.56‰和-11.16‰~8.2‰的范围内,来源为大气降水。根据舒卡列夫分类法,震前水样可划分为13种水化学类型,震后西山咀、圐圙朴隆等5个点采样点泉水的水化学类型发生变化。其中,乌拉山断裂带的水样以HCO₃-Ca型低矿化度地表水为主;色尔腾断裂带、狼山断裂带泉水受白垩系含水层影响,矿化度较高,富含HCO^-₃及SO^2-₄;桌子山一带受煤矿开采影响,水样以富SO^2-₄和Cl^-的高矿化度水为特征。地震前后TDS、阴、阳离子以及γNa/γCl、γ(SO₄+Cl)/γHCO₃、γHCO₃/γCl等毫克当量比值能够较好地反映地震。2015年4月15日阿左旗M_S5.8地震后,呼鲁斯太、迪延阿贵庙及八一井的水化学组成变化较大,对地震响应较为敏感。呼鲁斯太地区泉水的TDS稍有降低,但HCO^-₃在阴离子中所占比例有所增加,表明震后该地区含水层的泉水与较低矿化度的含碳酸盐岩含水层水发生了混合;八一井的TDS值有所增加,γNa/γCl比值有所降低,表明深部高矿化度水的混入;迪延阿贵庙水样的TDS稍有下降,但NaCl的相对含量较震前有所升高,表明有低矿化度NaCl水的混入。本工作不仅确定了该区水文地球化学背景,而且对地震监测和预测具有一定参考价值。     

Surface water and groundwater interactions in an extensively mined watershed,upper Schuylkill River,Pennsylvania, USA

Streams crossing underground coal mines may lose flow, whereas abandoned mine drainage (AMD) restores flow downstream. During 2005–2012, discharge from the Pine Knot Mine Tunnel, the largest AMD source in the upper Schuylkill River Basin, had near‐neutral pH and elevated concentrations of iron, manganese and sulphate. Discharge from the tunnel responded rapidly to recharge but exhibited a prolonged recession compared with nearby streams, consistent with rapid infiltration of surface water and slow release of groundwater from the mine complex. Dissolved iron was attenuated downstream by oxidation and precipitation, whereas dissolved CO₂ degassed and pH increased. During high flow conditions, the AMD and downstream waters exhibited decreased pH, iron and sulphate with increased acidity that were modelled by mixing net‐alkaline AMD with recharge or run‐off having low ionic strength and low pH. Attenuation of dissolved iron within the river was least effective during high flow conditions because of decreased transport time coupled with inhibitory effects of low pH on oxidation kinetics. A numerical model of groundwater flow was calibrated by using groundwater levels in the Pine Knot Mine and discharge data for the Pine Knot Mine Tunnel and West Branch Schuylkill River during a snowmelt event in January 2012. Although the calibrated model indicated substantial recharge to the mine complex took place away from streams, simulation of rapid changes in mine pool level and tunnel discharge during a high flow event in May 2012 required a source of direct recharge to the Pine Knot Mine. Such recharge produced small changes in mine pool level and rapid changes in tunnel flow rate because of extensive unsaturated storage capacity and high transmissivity within the mine complex. Thus, elimination of stream leakage could have a small effect on the annual discharge from the tunnel, but a large effect on peak discharge and associated water quality downstream. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Towards a classification of organic enrichment in marine sediments based on biogeochemical indicators

A nomogram is developed to show that pH, redox potentials (Eh_NHE) and measures of dissolved sulfides (H₂S + HS⁻ + S²⁻)(total free S²⁻) can be used to classify organic enrichment impacts in marine sediments. The biogeochemical cycle of sulfur in marine sediments is described to show that changes in macrobenthic infauna community structure associated with high levels of organic matter supply result from stress due to oxygen deficiency (hypoxia and anoxia) and toxic effects of S²⁻. The changes reflect enhancement of microbial sulfate reduction under conditions of high organic matter sedimentation and the progressive formation of hypoxic–anoxic conditions measured by decreased Eh_NHE and increased concentrations of S²⁻. The nomogram provides a basis for classification of the oxic status of marine sediments based on changes in inter-related biological and biogeochemical variables along an organic enrichment gradient.     

A Full-Scale Porous Reactive Wall for Prevention of Acid Mine Drainage

The generation and release of acidic drainage containing high concentrations of dissolved metals from decommissioned mine wastes is an environmental problem of international scale. A potential solution to many acid drainage problems is the installation of permeable reactive walls into aquifers affected by drainage water derived from mine waste materials. A permeable reactive wall installed into an aquifer impacted by low-quality mine drainage waters was installed in August 1995 at the Nickel Rim mine site near Sudbury, Ontario. The reactive mixture, containing organic matter, was designed to promote bacterially mediated sulfate reduction and subsequent metal sulfide precipitation. The reactive wall is installed to an average depth of 12 feet (3.6 m) and is 49 feet (15 m) long perpendicular to ground water flow. The wall thickness (flow path length) is 13 feet (4 m). Initial results, collected nine months after installation, indicate that sulfate reduction and metal sulfide precipitation is occurring. Comparing water entering the wall to treated water exiting the wall, sulfate concentrations decrease from 2400 to 4600 mg/L to 200 to 3600 mg/L; Fe concentrations decrease from 250 to 1300 mg/L to 1.0 to 40 mg/L; pH increases from 5.8 to 7.0; and alkalinity (as CaCO₃) increases from 0 to 50 mg/L to 600 to 2000 mg/L. The reactive wall has effectively removed the capacity of the ground water to generate acidity on discharge to the surface. Calculations based on comparison to previously run laboratory column experiments indicate that the reactive wall has potential to remain effective for at least 15 years.     

Der Kohlendioxid-Gehalt und die Kalzitsättigung der Ilm, einschließlich einiger Vergleichsuntersuchungen im Thüringer Raum

The CO₂ content, air saturation and calcite equilibrium of the River Ilm and some of its tributaries were analysed. CO₂ content was measured by degasing the CO₂ from water. The CO₂ level is a very sensitive indicator for a low pollution in oxygen saturated waters. Clean running waters have a CO₂ content close to the air saturation of 0.1–0.3 mg C l⁻¹. Ground water and springs are rich in CO₂. Polluted waters are characterised by higher CO₂ contents, also organic pollution can result in high values of CO₂. Carbon dioxide concentration of streams and brooks is limited by re-aeration.

The headwater region (softwater) of the River Ilm is unsaturated, the hard water in the middle- and underflow is oversaturated. In summer and autumn high saturation could be found, but without autochthonous calcite precipitation like in hard water lakes.     

The dynamic balance between organic acids and circumneutral groundwater in a large boreal peat basin

Large raised bogs and patterned fens cover 56% of the landscape in the Glacial Lake Agassiz region of northern Minnesota (USA). Organic acids supply most of the acidity in the surface water of the bogs, but groundwater upwelling from the underlying glacial deposits neutralizes these organic acids within deep peat. Substantial concentrations of organic acids also occur in the surface waters of fens mixed with variable amounts of inorganic solutes contributed by groundwater discharge. We used a triprotic analog model to determine the extent to which organic acids in fen and bog waters behave as strong or weak acids. The modeling approach optimized charge balance by calibrating estimates of mole site density in the DOC (dissolved organic carbon) of surface and pore waters with estimates of triprotic acid dissociation constants. Before the calibration process, all of the bog waters and 76% of the fen waters had more than +20% imbalance in charge balance. After calibration, more than 75% of all waters were electrochemically balanced within 20%. In the best calibration, the mole site denisty of bog DOC was estimated as 0.05 mmol/mmol C., approximately six times smaller than that estimated for fen DOC or the DOC in the fen deeper fen peats that underlie all bog landforms. The three modeled de-protonation constants were; pK_a1=3.0, pK_a2=4.5 and pK_a3=7.0 for the bog DOC, and; pK_a1=5.2, pK_a2= 6.5 and pK_a3=7.0 for the fen DOC. Bog DOC, behaves as a strong acid despite its small mole site density. The DOC in bog runoff can therefore theoretically acidify the surface waters in adjacent fens wherever these waters do not receive sufficient buffering alkalinity from active groundwater seepage.     

Seasonal and event-scale variations in solute chemistry for four Sierra Nevada catchments

Hydrobiogeochemical processes controlling stream water chemistry were examined in four small (<5 km²) catchments having contrasting bedrock lithologies in the western Sierra Nevada foothills of California. The Mediterranean climate with its cool/wet and hot/dry cycle produces strong seasonal patterns in hydrological, biological and geochemical processes. Stream water solutes fall into three general groups according to seasonal fluctuation in concentration: strong, rainy season minimum–dry season maximum (Cl⁻, SO₄²⁻, base cations); weak, rainy season minimum–dry season maximum (Si); and rainy season maximum–dry season minimum (NO₃⁻ and K⁺). Solute dynamics in soil solutions and stream water suggest that mixing of drainage waters from bedrock and soil sources regulate stream water solute concentrations. Patterns are further altered by the leaching of solutes accumulated in the soil over the summer period of desiccation and the temporal discoupling of nutrient cycles that occurs due to differences in the timing between vegetation growth (late spring) and leaching (early winter). Solute concentrations are remarkably similar between watersheds with varying bedrock types, with the exception of nitrate, sulfate and bicarbonate. Three watersheds have nitrogen-bearing metasedimentary bedrock that contributes to elevated nitrate concentrations in stream waters. Watersheds whose bedrock includes mineralized veins of sulfide and carbonate minerals similarly have greater sulfate and bicarbonate concentrations in stream water. Hydrobiogeochemical processes are highly dynamic at the seasonal and storm-event temporal scales and spatially complex at the watershed scale making management of stream water chemical composition, such as nitrate concentrations, very challenging.     

Acid-base status of soils in groundwater discharge zones — relation to surface water acidification

Critical load calculations have suggested that groundwater at depth of 2 m in Sweden is very sensitive to acid load. As environmental isotope studies have shown that most of the runoff in streams has passed through the soil, there is a risk in the near future of accelerated acidification of surface waters.

To assess the importance of the last soil horizon of contact before discharge, the upper 0–0.2m of soils in seven discharge zones were analysed for pools of base cations, acidity and base saturation. The sites were about 3–4 m² in size and selected from two catchments exposed to different levels of acid deposition.

The soils in the seven sites had high concentrations of exchangeable base cations and consequently high base saturation. The high correlation (r² = 0.74) between base saturation in the soils of the discharge zones and mean pH of the runoff waters suggested that the discharge zone is important for surface water acidification. The high pool of exchangeable base cations will buffer initially against the acid load. As the cation exchange capacity (meq dm⁻³) and base saturation were lower in the sites from the catchment receiving lower deposition, these streams may be more vulnerable to acidification in the near future. The high concentration of base cations in non-exchangeable fractions may also buffer against acidification as it is likely that some of these pools will become exchangeable with time.     

2012年6月30日新源Ms6.6地震前后北天山泥火山及温泉的水化学变化

2012年6月30日新源-和静M_s6.6地震前后,新疆北天山地区的泥火山及温泉出现了明显的水化学异常。在地震前后4天内,采集了两批泥火山和温泉水样品,测定了泥火山和温泉水样的水化学参数。资料表明,泥火山喷溢水属于低温、弱碱性咸水或盐水,水化类型为CI-Na,来源于储存在封闭构造中并与干旱海相、河湖相沉围岩发生了漫长而复杂水岩作用的大气降水。温泉水为中温、弱碱性SO₄·CI-Na型淡水,形成于地表水沿断裂深循环过程中的水岩作用。安集海泥火山出现同震喷溢,震后泥水温度(T)、总矿化度(TDS)、K+、Na+及Ca2+大幅上升;独山子、白杨沟及AM02泥火山为震前喷溢,独山子、白杨沟泥火山表现为T.TDS、EC、Na+、CI的升高和K⁺、Ca²⁺、Mg²⁺的降低;AM02泥火山K⁺、Mg⁺明显降低,Ca²⁺上升达223%。震后沙湾25号泉T降低7℃, TDS、电导率(EC)、K⁺、Na⁺、 Ca²⁺、 .Mg²⁺、CI^-及$SO_{4}^{2-}$升高。研究结果可用于北天山地区的地震趋势分析和改进利用各泥火山、温泉进行北天山地区地震活动性监测的水化学方法。     

Toxicity identification evaluation (TIE) of pore water of contaminated marine sediments collected from Hong Kong waters

Marine sediment can function both as a source and as a sink of marine chemical contaminants. The toxicity of contaminated marine sediment can be assessed by toxic evaluation of its pore water, the inter-particle water of sediment, because toxicants in the pore water may be bioavailable to marine organisms. In this study, the toxicity identification evaluation (TIE) was performed to identify the major toxicants in the pore water of marine sediment collected in Hong Kong waters. In Phase 1 TIE, the suspected toxicants were characterized as anions or organic compounds that are either oxidizable or filterable in alkaline medium. In Phase 2 TIE, the suspected toxicants were identified as sulfide (S²⁻) based on the reduction of toxicity due to lowering of sulfide concentrations by experimental manipulations. The mass balance and spiking analyses in Phase 3 confirmed that S²⁻ was one of the major toxicants and that some non-toxic unknown compounds measured by LC–MS, which was removed by C18 solid phase extraction, enhanced the toxicity of S²⁻ in the pore water samples.     

Anthropogenic and natural contributions to the rainfall chemistry of a mountainous area in the Cevennes National Park (Mont-Lozere, southern France)

Nine years of bulk precipitation chemistry data for a mountainous site in southern France are presented. The mean rainwater is of moderate acidity (pH 4.63, alkalinity −4 μEql⁻¹) even though there is high, non-marine, deposition of sulphur (near 20 kg ha⁻¹ year⁻¹). Based on the statistical characteristics of the data set, three major sources of elements are identified: long range pollution, Mediterranean sea salt aerosols and aeolian erosion dust, mainly from the Sahara. Most of the sulphur in the rainfall is present as neutral sulphate salts, owing to the latter being rich in alkaline minerals; this counteracts the strong acid input.     

Improved dissolved oxygen status following removal of exotic weed mats in important fish habitat lagoons of the tropical Burdekin River floodplain, Australia

The Burdekin delta floodplain, north Queensland, is highly modified for agricultural purposes. Riparian condition is very poor and exotic aquatic weeds dominate waterways. Historically, most streams and lagoons were highly seasonal, but those now used for the delivery of irrigation water maintain elevated flows and increased turbidity and nutrient loading. These factors have aided exotic weed growth and many major lagoons are covered by dense water hyacinth (Eichhornia crassipes) mats which greatly reduce dissolved oxygen levels, one of the most important water quality variables for aquatic fauna. Mechanical harvesting of water hyacinth from several of these lagoons resulted in rapid and substantial increases in dissolved oxygen saturation, and improved suitability of the habitat to support fish species. Decrease in dissolved oxygen as water passes sequentially through weed-infested lagoons, justified the approach of harvesting upstream lagoons first, however, the channels that connect these lagoons remain weed-infested and are still impacting upon downstream oxygen levels.     

Iodine-129 concentrations in marginal seas of the north Pacific and Pacific-influenced waters of the Arctic Ocean

Water sampling during the 1993 IV Russian–US Joint Expedition to the Bering and Chukchi Seas (BERPAC) indicates that Pacific Ocean burdens of the long-lived radionuclide ¹²⁹I are relatively low in the Pacific-influenced Arctic, particularly compared to high latitude waters influenced by the North Atlantic. These low concentrations occur despite the presence of potential submerged anthropogenic sources in the East Sea (Sea of Japan), and in the northwest Pacific Ocean, east of the Kamchatka Peninsula. The concentration of ¹²⁹I entering the Arctic Ocean through Bering Strait, 0.7×10⁸ atoms kg⁻¹, is only slightly higher than observed in deep Pacific waters. Similar concentrations (0.44–0.76×10⁸ atoms kg⁻¹) measured in Long Strait indicate no significant transfer of ¹²⁹I eastward into the Chukchi Sea in the Siberian Coastal Current from the Siberian marginal seas to the west. However, the concentrations reported here are more than an order of magnitude higher than the Bering Strait input concentration estimated (1.0×10⁶ atoms kg⁻¹) from bomb fallout mass balances, which supports other existing evidence for a significant atmospheric deposition term for this radionuclide in surface ocean waters. Near-bottom water samples collected in productive waters of the Bering and Chukchi Seas also suggest that sediment regeneration may locally elevate ¹²⁹I concentrations, and impact its utility as a water mass tracer. As part of this study, two deep ¹²⁹I profiles were also measured in the East Sea in 1993–1994. The near-surface concentration of ¹²⁹I ranged from 0.12 to 0.31×10⁸ atoms kg⁻¹. The ¹²⁹I concentration showed a steady decrease with depth, although because of active deep water ventilation, the entire 3000 m water column exceeded natural concentrations of the radionuclide. Atom ratios of ¹²⁹I/¹³⁷Cs in the East Sea also suggest an excess of ¹²⁹I above bomb fallout estimates, also possibly resulting from atmospheric deposition ultimately originating from nuclear facilities.     

Composition and sources of dissolved and particulate PAH in surface waters from the Rhone delta (NW Mediterranean)

PAH were determined in surface waters from the Rhone delta in winter and summer 1987. Both particulate and dissolved phases were analyzed by GC and GC/MS. Concentrations of major unsubstituted compounds associated with particles varied from a few to 20 ng l⁻¹, or from 0.42 to 6.0 μg g⁻¹. The seasonal variations reflected higher inputs in winter resulting from the presence of highly PAH-enriched particles. Tetra- and penta-cyclic PAH with MW 202 and 252 predominated, which reflected a significant origin from pyrolytic processes. A rapid decrease of the level of higher MW PAH was observed seawards in both seasons. Study of the tricyclic compounds and their alkylated homologues demonstrated a mainly fossil origin in winter, whereas in summer a high heterogeneity of particles was observed. PAH in the dissolved phase were found at concentrations up to 31 and 50 ng l⁻¹ in summer and winter, respectively. These levels were much higher than those encountered in the corresponding particulate phases. PAH with MW 178 and 202 predominated, and the alkylated homologues of the tricyclic compounds showed a major fossil orgin in winter and a mixed origin in summer. In winter dissolved PAH were transported through the delta into the marine environment without significant losses.