Trace metal levels in uncontaminated groundwater of a coastal watershed: importance of colloidal forms

Groundwater and surface water were collected using trace metal clean techniques from the upper glacial aquifer of West Neck Bay (Shelter Island) in eastern Long Island, NY, during the late spring and summer of 1999. The collection sites on Shelter Island are located in an area that is primarily residential and believed to have uncontaminated groundwater. Ultrafiltration was used to size-fractionate the dissolved (<0.45 microm) fraction into colloidal (1 kDa - 0.45 microm) and low molecular weight (<1 kDa) size pools. These fractions were analyzed for trace metals (Al, Ag, Cd, Cu, Mn, Pb, and Zn), organic carbon, and inorganic nutrients (NH4, NO3, PO4). The levels of metals and organic carbon in the groundwater were as low as those found in the open ocean, far removed from anthropogenic inputs. These findings corroborate the need to apply trace metal clean techniques in the determination of metal levels in uncontaminated groundwater. A significant fraction of dissolved metals (22-96%) and organic carbon (approximately 40%) in the groundwater and in surface waters of the Bay was found to be associated with colloids. The significance of the metal association with the colloidal fraction decreased in the order of Al > Cu > Ag > Zn = Cd = Mn and appeared to be dependent on the affinities of these metals for humic substances. In contrast, NO3 and NH4 were found to be almost entirely (approximately 98-99%) in the low molecular weight size fraction. Metal/aluminum and metal/carbon ratios measured in the colloids were similar to those reported for humic substances and significantly different from those of soils. This suggests that colloidal particles might originate from humic materials as opposed to purely inorganic minerals. These results indicate the need to consider the colloidal fraction in the fate and mobility of metals in groundwater and that, despite the low levels of organic matter (<50 microM of DOC) measured in groundwater, some groundwater colloids appear to be organic in nature.     

Dissolved trace element concentrations in the East River-Long Island Sound system: relative importance of autochthonous versus allochthonous sources

Dissolved trace metal (Ag, Cd, Cu, Fe, Ni, Pb, and Zn), inorganic nutrient (NO3, NH4, PO4, H4SiO4), and DOC concentrations were measured at 43 stations during low (July 2000) and high (April 2001) river discharge conditions in surface waters of Long Island Sound (LIS). To evaluate the impact of fluvial sources to the total metal budget of the sound, samples were collected from major tributaries discharging into LIS (Thames, Quinnipiac, Housatonic, Connecticut, and East Rivers). To compare LIS with other coastal embayments, samples were also collected from five LIS coastal embayments (Manhassett Bay, Huntington Harbor, Oyster Bay, Hempstead Harbor, and Port Jefferson Harbor), which are monitored by the U.S. National Status and Trends Program. Metal and nutrient distributions identified two biogeochemical regimes within LIS: an area of relatively high nutrient and metal concentrations in the East River/Narrows region in western LIS and an area in the eastern region of the sound that had comparatively lower concentrations. Mass balance estimates indicated that, during low flow conditions, the East River was the dominant allochthonous source of most trace metals (Ag, Cd, Cu, Ni, Zn) and inorganic nutrients (NO3 and PO4); during high flow conditions, the most influential source of these constituents was the Connecticut River. Mass balance estimates also evidenced a large autochthonous source of Cu, Ni, and Zn, as their spatial distributions displayed elevated concentrations away from point sources such as the East River. Principal component analysis suggested that metal and nutrient distributions in the LIS system were influenced by different seasonal processes: remobilization from contaminated sediments, anthropogenic inputs from sewage discharges and phytoplankton scavenging during the spring freshet, and benthic remobilization during summer conditions.     

Sedimentological control on Mn, and other trace elements, in groundwater of the Bengal delta

To reveal what controls the concentration and distribution of possibly hazardous (Mn, U, Se, Cd, Bi, Pb) and nonhazardous (Fe, V, Mo, PO(4)) trace elements in groundwater of the Bengal delta, we mapped their concentrations in shallow groundwater (<60 mbgl) across 102 km(2) of West Bengal. Only Mn is a potential threat to health, with 55% of well water exceeding 0.3 mg/L, the current Indian limit for drinking water in the absence of an alternate source, and 75% exceeding the desirable limit of 0.1 mg/L. Concentrations of V are <3 μg/L. Concentrations of U, Se, Pb, Ni, Bi, and Cd, are below WHO guideline values. The distributions of Fe, Mn, As, V, Mo, U, PO(4), and δ(18)O in groundwater reflect subsurface sedimentology and sources of water. Areas of less negative δ(18)O reveal recharge by sources of evaporated water. Concentrations of Fe, As, Mo, and PO(4) are high in palaeo-channel groundwaters and low in palaeo-interfluvial groundwaters. Concentrations of U, V, and Mn, are low in palaeo-channel groundwaters and high in palaeo-interfluvial groundwaters. Concentrations of Fe and Mn are highest (18 and 6 mg/L respectively) at dual reduction-fronts that form strip interfaces at depth around the edges of palaeo-interfluvial aquifers. The fronts form as focused recharge carries dissolved organic carbon into the aquifer margins, which comprise brown, iron-oxide bearing, sand. At the Mn-reduction front, concentrations of V and Mo reach peak concentrations of 3 μg/L. At the Fe-reduction front, concentrations of PO(4) and As reach concentrations 3 mg/L and 150 μg/L respectively. Many groundwaters contain >10 mg/L of Cl, showing that they are contaminated by Cl of anthropogenic origin and that organic matter from in situ sanitation may contribute to driving reduction.     

Has submarine groundwater discharge been overlooked as a source of mercury to coastal waters?

We measured the mercury (Hg) in groundwater, aquifer sediments, and surface water in Waquoit Bay (Massachusetts) and found that this toxic metal (range: <3.2-262 pM) was being released within the subterranean estuary, with similarly high levels (range: 18-256 pM) found in the surface waters of the bay. None of the dissolved species (DOC, chloride, and Fe) normally observed to influence Hg partitioning correlated well with the observed Hg concentrations. It was hypothesized that this was in part due to the variable loading in time and space of Hg onto the aquifer sands in combination with the seasonality of groundwater flow through the aquifer. Aquifer sediment samples from the study site ranged from <1 to 12.5 pmol of Hg/g of sediment, suggesting log Kd values on the order of 1. We hypothesize that this was due to the low organic carbon content typical of the aquifer sediments. Last, itwas estimated that submarine groundwater discharge supplied 0.47-1.9 nmol of Hg m(-2) day(-1) to the bay, which is an order of magnitude higher than the atmospheric deposition rate for the northeastern U.S.     

Oral intake of cadmium,cobalt, copper,iron, lead,nickel, manganese and zinc in the University student's diet

A duplicate diet meal study was carried out with a group of university students living in a hostel, in order to estimate the intake of Zn, Cd, Co, Cu, Fe, Mn, Ni and Pb. Zn, Cu, Fe, Mn and Ni were determined by flame atomic absorption spectrophotometry and Cd, Co and Pb by graphite furnace atomic absorption spectrophotometry after a nitric acid wet digestion procedure. The estimated intake values from the contents of breakfast, lunch, dinner and drinks were compared with the values of the Provisional Tolerable Daily Intake (PTDI) in the case of Cd and Pb, Recommended Dietary Allowances (RDA) of Co, Fe and Zn and Estimated Safe and Adequate Dietetic Daily Intake (ESADDI) of Cu and Mn. Neither excessive intake of Pb and Cd nor deficiencies in Zn, Co, Fe, Mn or Ni were observed, but Cu intake was lower than the ESADDI.     

岩藻聚糖中重金属元素脱除方法的研究

研究采用螯合剂及超滤技术脱除岩藻聚糖中重金属元素的方法。在提取岩藻聚糖工艺中添加不同浓度的EDTA 二钠和植酸溶液,对所制备的岩藻聚糖采用电感耦合等离子体- 质谱技术(ICP-MS)及氢化物- 原子荧光光谱法(HGAFS)检测其Mg、Ca、Fe、Mn、Cu、Zn、Ag、Cd、Ba、Pb、As、Hg 元素的含量。研究表明,在提取工艺中加入1.0 × 10-2mol/L EDTA 二钠可以有效地降低岩藻聚糖中Mg、Ca、Mn、Zn、As、Ag、Cd、Pb等元素的残留量,但没有减少Hg、Fe、Cu、Ba 元素的残留量;而提取工艺中加入0.10mol/L 植酸仅对减少Ag、Cd 和Zn 元素的残留量有一定的效果。通过对岩藻聚糖进行As、Hg 富集处理,研究在酸处理后采用超滤脱除重金属元素的效果,结果表明,各实验组均未检出As 元素,但对Hg 元素没有效果。因此,在提取岩藻聚糖的工艺中添加一定浓度的EDTA 二钠或在纯化过程中经酸处理后采用超滤脱除技术均可显著减少岩藻聚糖制品中重金属元素的残留量,从而制备高质量的岩藻聚糖。     

Trace elements and metals in farmed sea bass and gilthead bream from Tenerife Island, Spain

The aim of this study was to determine the levels of metals (Ca, K, Na, Mg) and trace metals (Ni, Fe, Cu, Mn, Zn, Pb, Cd) in two fish species (gilthead bream [Sparus aurata] and sea bass [Dicentrarchus labrax]) collected from fish farms located along the coast of Tenerife Island. Ca, K, Na, Mg, Fe, Cu, Zn, and Mn were measured by flame atomic absorption spectrometry, whereas Pb, Cd, and Ni were determined using graphite furnace atomic absorption spectrometry. Mean Fe, Cu, Mn, and Zn contents were 3.09, 0.59, 0.18, and 8.11 mg/kg (wet weight) in S. aurata and 3.20, 0.76, 0.24, and 10.11 mg/kg (wet weight) in D. labrax, respectively. In D. labrax, Ca, K, Na, and Mg levels were 1,955, 2,787, 699.7, and 279.2 mg/kg (wet weight), respectively; in S. aurata, they were 934.7, 3,515, 532.8, and 262.8 mg/kg (wet weight), respectively. The Pb level in S. aurata was 7.28 ± 3.64 μg/kg (wet weight) and, in D. labrax, 4.42 ± 1.56 μg/kg (wet weight). Mean Cd concentrations were 3.33 ± 3.93 and 1.36 ± 1.53 μg/kg (wet weight) for D. labrax and S. aurata, respectively. All Pb and Cd levels measured were well below the accepted European Commission limits, 300 and 50 μg/kg for lead and cadmium, respectively.     

Geochemical cycling of arsenic in a coastal aquifer

Biogeochemically modified pore waters from subterranean estuaries, defined as the mixing zone between freshwater and saltwater in a coastal aquifer, are transported to coastal waters through submarine groundwater discharge (SGD). SGD has been shown to impact coastal and perhaps global trace metal budgets. The focus of this study was to investigate the biogeochemical processes that control arsenic cycling in subterranean estuaries. Total dissolved As, as well as a suite of other trace metals and nutrients, were measured in a series of wells and sediment cores at the head of Waquoit Bay, MA. Dissolved As ranged from below detection to 9.5 microg/kg, and was associated with plumes of dissolved Fe, Mn, and P in the groundwater. Sedimentary As, ranging from 360 to 7500 microg/kg, was highly correlated with sedimentary Fe, Mn, and P. In addition, amorphous Fe (hydr)oxides were more efficient scavengers of dissolved As than the more crystalline forms of solid-phase Fe. Given that dissolved As in the surface bay water was lower than within the subterranean estuary, our results indicate that the distribution and type of Fe and Mn (hydr)oxides in coastal aquifers exert a major influence on the biogeochemical cycling of As in subterranean estuaries and, ultimately, the fate of groundwater-derived As in marine systems influenced by SGD.     

Cadmium,lead and some other trace elements in Larch Bolete mushrooms (Suillus grevillei) (Klotzsch) Sing., collected from the same site over two years

The aim of this study was to examine the status of some trace metals accumulated in the flesh of Suillus grevillei mushrooms collected from the same site over two successive years. Total Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn contents of fruiting bodies were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) with ultrasonic cross-flow nebuliser. A difference (p < 0.05) was found in the contents of Cd, Cr, Cu, Fe, K, Na, Ni, Pb, Rb and Sr in caps and Fe, Na, P and Rb (p < 0.05) in stipes (Ag, Cd, Co, Cr, Ni and Pb were not determined in stipes). Natural fluctuations in trace elements’ content of Suillus grevillei collected from the same site over time is a variable that needs to be considered when assessing minerals’ nutritional status of mushrooms.     

Trace metals in squidIllex argentinus

Summary The determination of the cadmium, silver, lead, copper, zinc, manganese, iron and mercury levels is reported in edible and inedible tissues of the squid speciesIllex argentinus, caught in the region of the Continental Shelf of Argentina in 1986.The methods of determination were flame AAS for Cd, Ag, Pb, Cu, Zn, Mn, and Fe and cold-vapour AAS for Hg. The mean values obtained were related to the wet weight (mg/kg). Th edible parts of the squid (skinless mantle and arms/crone) were 0.067 and 0.053 for Cd, 0.07 and 0.07 for Ag, 0.11 and 0.15 for Pb, 1.7 and 3.4 for Cu, 12 and 19 for Zn, 0.14 and 0.12 for Mn, 1.0 and 1.2 for Fe, and 0.012 for Hg (mantle only). Much higher levels of the metals investigated have been found in the liver, intestines, skin, eyes, arrow and the ink like liquid of the squid.

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Spurenmetalle in Tintenfisch (Illex argentinus)

Zusammenfassung Cadmium, Silber, Blei, Kupfer, Zink, Mangan, Eisen und Quecksilber wurden in den eßbaren und nichteßbaren Geweben von Tintenfisch (Illex argentinus), gefangen 1986 in dem Continental Shelf of Argentina, bestimmt. Die Meßmethoden wurden für Cd, Ag, Pb, Cu, Zn, Mn und Fe durch Flammen-Atomabsorption und für Quecksilber durch Kaltdampf-Atomabsorption bestimmt. Die Mittelwerte waren für die eßbaren Teile, auf Naßgewicht (mg/kg) berechnet — für den hautlosen Mantel und Arme: 0,067 und 0,053 für Cd, bzw. 0,07 und 0,07 für Ag, 0,11 und 0,15 für Pb, 1,7 und 3,4 für Cu, 12 und 19 für Zn, 0,14 und 0,12 für Mn, 1,0 und 1,2 für Fe, und 0,012 für Hg (Mantel allein). Höhere Werte der Metalle wurden in Leber, Eingeweide, Haut, Augen und in der tintenähnlichen Flüssigkeit gefunden.

     

Thermally induced changes in metal solubility of contaminated soils is linked to mineral recrystallization and organic matter transformations

Soils are biogeochemical systems under continual modification by biological and chemical processes. Trace element solid-solution partitioning is thus influenced by long-term changes to these solid phases. We study Pb, Cd, Zn, and Cu solution speciation and solid-phase dynamics in two soils of volcanic origin (Te Akatea and Egmont, high in noncrystalline aluminosilicates), an oxisol from Brazil (Oxisol, high in oxides of Al and Fe), and several sludge-treated soils (labeled NYS soils, high in organic materials). Total soluble (by ICP) and labile (by ASV) concentrations of Pb, Cd, Zn, and Cu were determined after incubation of the soils for about 1.5 yr at room (23 degrees C) and elevated (70 degrees C) temperatures. Changes occurring to the solid phases were monitored by FTIR and extraction with oxalate and pyrophosphate. It is shown that induced hydrolysis or decomposition of organic materials in soils results in increases in both labile and total soluble concentrations of Pb, Cd, Cu, and Zn in solution. Labile and total soluble concentrations of Cu and Zn increase concomitantly with dissolved organic carbon (DOC); the nonlabile soluble fraction also increases with increasing DOC. Similarly, the concentration of Cd and Pb in solution increases with increasing DOC; however, most soluble Cd and Pb is asv-labile. Only in the Egmont soil (mineralogy dominated by proto-imogolite allophane) was reduced Pb solubility observed after prolonged equilibration and heating. Lead solubility increased after partial crystallization of amorphous minerals in the Te Akatea and the Oxisol. Thus, for most of the metal-soil systems studied, prolonged thermal treatment at 70 degrees C increased total soluble and asv-labile metals, suggesting that aging effects on metals in contaminated soils could release metals to labile forms in some cases.     

西施舌可食部分微量元素分析与评价

分析西施舌可食部分不同部位微量元素含量,评价其营养价值和重金属污染情况。用硝酸-高氯酸消化法消解组织,用电感耦合等离子体发射光谱(inductively coupled plasma atomic emission spectrometry technique,ICP-AES)法测定黄海日照、东海漳州、北部湾越南某海区(毗邻广西北海)3个地区西施舌闭壳肌、外套膜、斧足、鳃、内脏团5个部位(组织/器官)的12种元素。比较Ag、As、Cd、Co、Cr、Cu、Fe、Mn、Pb、Se、Sn、Zn元素在不同地域和不同部位的分布和含量。结果显示：10种元素的加标回收率为78.3%～112.1%,相对标准偏差为0.16%～7.46%;西施舌富含Fe、Zn、Mn、Cu、Se等人体必需的微量元素,Ag和Sn元素含量低;多数元素在同域不同部位的含量存在显著差异(P＜0.05),日照西施舌外套膜、内脏团Fe的含量显著(P＜0.05)高于同域其他组织及漳州、越南西施舌所有组织;西施舌As、Cd的含量超过国家卫生限量标准,但Cd的含量低于世界卫生组织、澳大利亚、香港的限量标准。     

The effects of season and sex in the metal levels of mature common cuttlefish (Sepia officinalis) in Mersin Bay, Northeastern Mediterranean

The effects of sex and season on metal levels of the mantle of the common cuttlefish that was caught from Mersin Bay were evaluated. The annual range of mantle length (ML), total length (TL), and weight of common cuttlefish specimens were 110 to 183 mm, 380 to 581 mm, and 150.24 to 477.13 g, respectively. The annual range of metal levels in the mantle tissue of common cuttlefish were: 2.34 to 3.89 μg Cd g(-1), 0.30 to 0.63 μg Cr g(-1), 0.15 to 0.54 μg Pb g(-1), 2.35 to 14.90 μg Cu g(-1), 23.22 to 51.88 μg Zn g(-1), and 5.12 to 10.65 μg Fe g(-1). Cu levels of females were significantly higher (P < 0.05) than those found in male throughout all the seasons while Pb levels were lower (P < 0.05) in males than females. Cr levels in the mantle tissue of cuttlefish did not change throughout the seasons. On the contrary, Cd, Pb, Cu, Zn, and Fe levels in the mantle tissue of cuttlefish changed throughout all the seasons. The highest Cd, Zn, and Fe levels were obtained in spring while the highest Cu levels were obtained in autumn. It was also found out that this species was rich in terms of metal levels, particularly, Cd, Cu, Zn, and Fe. It was found out that the mantle tissue of the common cuttlefish, Sepia officinalis, which was caught from Mersin Bay, was contaminated with Cd in all the seasons.     

Inorganic geochemistry and redox dynamics in bank filtration settings

Bank filtration induces flow of surface water through a hydraulically connected aquifer by excess pumping from a production well in the aquifer. This review presents the four main geochemical processes relevant for inorganic geochemistry, with a focus on iron (Fe) and manganese (Mn), during bank filtration: reduction near the bank, oxidation near the production well, carbonate dissolution, and sorption to aquifer materials. Physical and transport processes affect these geochemical processes and influence the redox state of the infiltrate. The presence of Fe and Mn in bank infiltrate is directly related to its redox status and can necessitate drinking water treatment after extraction. Long-term, in situ sequestration of Fe and Mn requires precipitation of oxide or carbonate solids, since a sorption front can breakthrough at the production well.     

Trace metal concentrations and water solubility in size-fractionated atmospheric particles and influence of road traffic

The abundance and the behavior of metals (Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Se, Ag, Cd, Sn, Ba, Pt, Hg, and Pb) and ions (Na+ K+ Mg2+ Ca2+, NH4+, Cl-, NO3-, SO4(2-), PO4(3-), and oxalate) in size-fractionated atmospheric particulate matter (PM) were studied in the U. K. and Ireland at four observation sites simulating extreme degrees of vehicular-traffic influence in the environment. Trace metals in urban PM showed distinct types of size-fractionated behavior depending on the particle sources from which they originate. In coarse PM (1.5 < Dp < 3.0 microm) the concentrations of copper, barium, and iron correlated closely across over 2 orders of magnitude in urban air, which is seen as evidence that major portions of transition metals (Cu, Ba, Fe, and Mn) are released through abrasive vehicular emissions, particularly the wear of brake linings. Further results are strongly indicative of a decoupling of coarse iron and calcium, the former arising predominantly from vehicles, the latter from soil resuspension. In fine PM (Dp < 0.5 microm), several combustion and secondary sources of particulates were identified, but these were much less unique in terms of elemental fingerprints. An analysis of the water solubility of trace metals yielded that solubility varies considerably with element and, to a lesser extent, with particle size. Notable differences were found to the elemental water solubilities determined in previous work, partially explained by differences in extraction procedures.     

Levels of essential and non-essential metals in leaves of the tea plant (Camellia sinensis L.) and soil of Wushwush farms,Ethiopia

Five tea clones of the Camellia assamica variety grown in Wushwush tea plantation farms, Ethiopia, were analyzed for their contents of essential, non-essential and toxic metals (K, Ca, Mg, Fe, Mn, Cu, Zn, Na, Cd and Pb) by atomic absorption flame emission spectroscopy. Both the tea leaves and the soils of the study farms showed similar accumulation patterns in their contents of the studied macronutrients. Among the macronutrient metals, K was the most abundant element in the tea leaves (17.7–24.8 mg/g) and the soils (7.14–9.73 mg/g). Mn was the predominant micronutrient heavy metal in the tea leaf tissues ranging between 501 and 1281 mg/kg. Level of Fe (29.6–100 mg/kg) in the leaf tissue was found to be the second most abundant micronutrient next to Mn whereas concentrations of Cu and Co were relatively lower both in the soil and tea samples. The toxic heavy metals Pb and Cd in the leaf tissues were present at levels too low to be detected by the analytical technique used in this study. The soils were found to be acidic (pH 5.04–5.49) with high organic matter (5.48–6.02%). Fe was the most abundant metal followed by Mn, Na and Zn in the soils. Unlike the tea leaves, the soils were found to contain traces of the toxic metal, Cd (0.02–1.10 mg/kg). The levels of most of the metals determined in this study compared well with those reported for tea leaves from some other parts of the world.     

High concentrations of essential and toxic elements in infant formula and infant foods – A matter of concern

This study assessed concentrations in and intake of toxic and essential elements from formulas and foods intended for infants during their first 6 months of life. Concentrations of the essential elements Ca, Fe, Zn, Mn and Mo were significantly higher in most formulas than in breast milk. Daily intake of Mn from formula varies from ten up to several hundred times the intake of the breast fed infant, levels that may be associated with adverse health effects. One portion of infant food provided significantly more Fe, Mn, Mo, As, Cd, Pb and U than one feeding of breast milk, but less Ca, Cu and Se. Rice-based products in particular contained elevated As concentrations. Drinking water used to mix powdered formula may add significantly to the concentrations in the ready-made products. Evaluation of potentially adverse effects of the elevated element concentrations in infant formulas and foods are warranted.     

Trace metal levels in mushroom samples from Ordu,Turkey

The concentrations of Fe, Mn, Zn, Cu, Pb, Cd, Cr, Ni in mushroom species of Turkish origin were determined by atomic absorption spectrometry after microwave digestion. The mushrooms were collected from Ordu, Turkey. The highest Fe level was 628 mg/kg in Mycena inclinata. The highest Mn levels was 103 mg/kg in Coprinus comatus. Zn level was 162 mg/kg in Panellus stipticus. Cu level was 86.2 mg/kg in M. inclinata. Pb level was 11.4 mg/kg in P. stipticus. Cd level was 1.6 mg/kg in Panaeolus campanulatus. Cr level was 4.4 mg/kg in C. comatus and Ni level was 21.6 mg/kg in M. inclinata.     

Adsorption of Cu, Cd, and Ni on goethite in the presence of natural groundwater ligands

The adsorption of copper, cadmium, and nickel on goethite was examined in natural groundwater samples from an infiltration site of the river Glatt at Glattfelden (Switzerland). Unfractionated dissolved organic matter was used at its natural concentrations. Metal concentrations were close to environmental conditions. Cu, Cd, and Ni presented the typical pH adsorption edge of cations. The major influence on metal adsorption was due to a strong organic ligand L(I), which inhibited adsorption of Cu, Cd, and Ni in the alkaline pH region. Complexation of Cu, Cd, and Ni by the natural organic ligands was described with a model defining a minimum number of discrete ligands: a strong ligand L(I) at low concentration and additional weaker ligands with higher concentrations. The adsorption of Cu, Cd, and Ni on the goethite surface in the presence of the natural organic ligands was adequately described by considering only surface complexation and complexation in solution by organic ligands. No ternary complexes had to be invoked in the model. The major effect was complexation by the strongest ligand, whereas interactions with other cations and anions had only a minor influence. Competition reactions between Cu and Ni for complexation with the same strong ligand L(I) were observed.     

Factors affecting the presence of dissolved glutathione in estuarine waters

We investigated factors influencing the presence of the thiol glutathione (GSH) in estuarine waters. Our study addressed thiol phase-association, the biological release from algal cultures, and the role of copper in both thiol release and preservation. Our measurements in three diverse estuaries in the continental United States (San Diego Bay, Cape Fear Estuary, and Norfolk Estuary) show that dissolved GSH, present at sub-nanomolar levels, is preferentially partitioned into the ultra-filtrate fraction (<1 kDa) in comparison with dissolved organic carbon (DOC). Concentrations of GSH generally increased with increases in total copper (Cu)levels, although large variability was observed among estuaries. In 30-h exposure experiments, release of dissolved GSH from the diatom Thalassiosira weissflogii into organic ligand-free experimental media was a strong function of added Cu concentration. The released GSH increased from about 0.02 to 0.27 fmol/cell as Cu was increased from the background level (0.5 nM) to 310 nM in the modified Aquil media. However, excretion of GSH was lower (up to 0.13 fmol/cell) when cells were grown in surface waters of San Diego Bay, despite much higher total Cu concentrations. Experiments conducted in-situ in San Diego Bay water indicated that high concentrations of added Cu destabilized GSH, while both Mn(II) and natural colloids promoted GSH stability. In contrast, laboratory experiments in synthetic media indicated that moderate levels of added Cu enhanced GSH stability.