A study of arsenic,iron and other dissolved ion variations in the groundwater of Bishnupur District,Manipur, India

The presence of arsenic (As) in groundwater and its effect on human health has become an issue of serious concern in recent years. The present study assessed the groundwater quality of the Bishnupur District, Manipur, with respect to drinking water standards. Higher concentrations of pH, iron and phosphate were observed at several locations. Phosphate and iron levels were highest in the pre-monsoon, followed by monsoon and post-monsoon seasons. The arsenic concentrations were highest during post-monsoon (1–200 μg L⁻¹) as compared to pre-monsoon (1–108 μg L⁻¹) and monsoon (2–99 μg L⁻¹). Kwakta and Ngakhalawai show higher levels of arsenic concentration as compared to the prescribed World Health Organization (WHO) and Bureau of Indian Standards (BIS) norms. Arsenic showed a strong positive correlation with phosphate and negative correlation with sulphate, suggesting a partial influence of anthropogenic sources. The study suggests that the Bishnupur area has an arsenic contamination problem, which is expected to increase in the near future.     

Environmental geochemistry of high arsenic groundwater at western Hetao plain, Inner Mongolia

Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO₃⁻ and SO₄²⁻ are relatively low, while the concentrations of DOC, NH₄⁺, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe₂O₃, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.     

Partition of arsenic in soils sediments and the origin of naturally elevated concentrations in groundwater of the southern pampa region (Argentina)

Excessive arsenic concentrations above the Argentinean and WHO guidelines for drinking water (10 μg L⁻¹) affects shallow aquifers of the southern Pampean Plain (Argentina) hosted in the Pampean and the Post Pampean formations (loess and reworked loess; Plio-Pleistocene–Holocene). Health problems related to high As concentrations in drinking waters are known as Endemic Regional Chronic Hydroarsenicism. Hydrochemistry of shallow groundwaters and soil geochemistry were investigated aiming to (1) understand the partition of As in the solid phase and its relationship with unacceptable As concentrations in waters, (2) identify the provision source of As to groundwaters. Only 5% of the samples had As concentrations <10 μg L⁻¹; in 27% As concentrations ranged from 10 to 50 μg L⁻¹ and in 58% it reached 60–500 μg L⁻¹. The coarse fraction (50–2,000 μm) hosts about 27% of the total As in the solid phase, being positively correlated to Ba (p < 0.01; r ² = 0.93). About 70% is included in the <2 μm fraction and had positive correlations of As–Fe (p < 0.05; r ² = 0.85) and As–Cr (p < 0.05; r ² = 0.68). Soils and sediment sand fractions of vadose zones are the primary sources of As in shallow groundwater while adsorption–desorption processes, codisolution–coprecipitation, and evaporation during the dry seasons raise As concentrations in waters exceeding the guideline value for drinking water.     

Distribution and enrichment of trace metals in marine sediments of Bay of Bengal,off Ennore,south-east coast of India

In order to avoid the pollution of trace metals in marine environment, it is necessary to establish the data and understand the mechanisms influencing the distribution of trace metals in marine environment. The concentration of heavy metals (Fe, Mn, Cr, Cu, Ni, Pb, Zn, Co and Cd) were studied in sediments of Ennore shelf, to understand the metal contamination due to heavily industrialized area of Ennore, south-east coast of India. Concentration of metals shows significant variability and range from 1.7 to 3.7% for Fe, 284–460 μg g⁻¹ for Mn, 148.6–243.2 μg g⁻¹ for Cr, 385–657 μg g⁻¹ for Cu, 19.8–53.4 μg g⁻¹ for Ni, 5.8–11.8 μg g⁻¹ for Co, 24.9–40 μg g⁻¹ for Pb, 71.3–201 μg g⁻¹ for Zn and 4.6–7.5 μg g⁻¹ for Cd. For various metals the contamination factor (CF) and geoaccumulation index (I _geo) has been calculated to assess the degree of pollution in sediments. The geoaccumulation index shows that Cd, Cr and Cu moderately to extremely pollute the sediments. This study shows that the major sources of metal contamination in the Ennore shelf are land-based anthropogenic ones, such as discharge of industrial wastewater, municipal sewage and run-off through the Ennore estuary. The intermetallic relationship revealed the identical behavior of metals during its transport in the marine environment.     

The impact of over 100 years of wildfires on mercury levels and accumulation rates in two lakes in southern California,USA

In southern California, USA, wildfires may be an important source of mercury (Hg) to local watersheds. Hg levels and Hg accumulation rates were investigated in dated sediment cores from two southern California lakes, Big Bear Lake and Crystal Lake, located approximately 40-km apart. Between 1895 and 2006, fires were routinely minimized or suppressed around Big Bear Lake, while fires regularly subsumed the forest surrounding Crystal Lake. Mean Hg concentrations and mean Hg accumulation rates were significantly higher in Crystal Lake sediments compared to Big Bear Lake sediments (Hg levels: Crystal Lake 220 ± 93 ng g⁻¹, Big Bear Lake 92 ± 26 ng g⁻¹; Hg accumulation: Crystal Lake 790 ± 1,200 μg m⁻² year⁻¹, Big Bear 240 ± 54 μg m⁻² year⁻¹). In Crystal Lake, the ratio between post-1965 and pre-1865 Hg concentrations was 1.1, and several spikes in Hg levels occurred between 1910 and 1985. Given the remote location of the lake, the proximity of fires, and the lack of point sources within the region, these results suggested wildfires (rather than industrial sources) were a continuous source of Hg to Crystal Lake over the last 150 years.     

Geo-chemical Behavior of Uranium in the Sambhar Salt Lake, Rajasthan (India): Implications to "Source" of Salt and Uranium "Sink"

Among several salt lakes in the Thar Desert of western India, the Sambhar is the largest lake producing about 2 × 10⁵ tons of salt (NaCl) annually. The “lake system” (lake waters, inflowing river waters, and sub-surface brines) provides a unique setting to study the geo-chemical behavior of uranium isotopes (²³⁸U, ²³⁴U) in conjunction with the evolution of brines over the annual wetting and evaporation cycles. The concentration of ²³⁸U and the total dissolved solids (TDS) in lake water increase from ~8 μg L⁻¹ and ~8 g L⁻¹ in monsoon to ~1,400 μg L⁻¹ and 370 g L⁻¹, respectively, during summer time. The U/TDS ratio (~1 μg g⁻¹ salt) and the ²³⁴U/²³⁸U activity ratio (1.65 ± 0.05), however, remain almost unchanged throughout the year, except when U/TDS ratio approaches to 3.8 at/or beyond halite crystallization. These observations suggest that uranium behaves conservatively in the lake waters during the annual cycle of evaporation. Also, uranium and salt content (TDS) are intimately coupled, which has been used to infer the origin and source of salt in the lake basin. Furthermore, near uniform ratios in evaporating lake waters, when compared to the ratio in seawater (~0.1 μg g⁻¹ salt and 1.14 ± 0.02, respectively), imply that aeolian transport of marine salts is unlikely to be significant source of salt to the lake in the present-day hydrologic conditions. This inference is further consistent with the chemical composition of wet-precipitation occurring in and around the Sambhar lake. The seasonal streams feeding the lake and groundwaters (within the lake’s periphery) have distinctly different ratios of U/TDS (2–69 μg g⁻¹ salt) and ²³⁴U/²³⁸U (1.15–2.26) compared to those in the lake. The average U/TDS ratio of ~1 μg g⁻¹ salt in lake waters and ~19 μg g⁻¹ salt in river waters suggest dilution of the uranium content by the recycled salt and/or removal processes presently operating in the lake during the extraction of salt for commercial use. Based on mass-balance calculations, a conservative estimate of "uranium sink" (in the form of bittern crust) accounts for ~5 tons year⁻¹ from the lake basin, an estimate similar to its input flux from rivers, i.e., 4.4 tons year⁻¹.     

Adsorption, desorption and oxidation of arsenic affected by clay minerals and aging process

 Adsorption/desorption and oxidation/reduction of arsenic at clay surfaces are very important to the natural attenuation of arsenic in the subsurface environment. Although numerous studies have concluded that iron oxides have high affinities for the adsorption of As(V), very little experimental work has addressed the arsenic attenuation capacities of different clay minerals and aging process affecting the transformation of arsenic. The abundance of clay minerals in a variety of geochemical environments and their influence on adsorption of contaminants suggests a need for more experimental work to characterize the adsorption desorption, and oxidation of arsenic on clay minerals. In this investigation three types of clay mineral were studied: the 1 : 1 layer clays [halloysite (IN), sedimentary M-kaolinite, and weathered EPK-kaolinite]; the 2 : 1 layer clays [illite (MT) and illite/montmorillonite (MT)]; the 2 :>: 1 layer clay [chlorite (CA)]. The halloysite and the chlorite had much greater As(V) adsorption (25–35 folds) than the other clay minerals. The clay minerals had lower As(III) adsorption than As(V) adsorption, and the adsorption was affected by pH. Desorption of arsenic from the clay minerals was significantly influenced by the aging process. The quantities of extractable As(III) and As(V) decreased with increasing aging time. The results demonstrated that oxidation of As(III) to As(V) occurred on the clay surfaces, whereas reduction of As(V) to As(III) was not found in any of the clay minerals studied. The oxidation of As(III) was affected by the types of clay and aging time. Received: 22 March 1999 · Accepted: 15 April 1999     

<Superscript>210</Superscript>Pb-derived Sedimentation Rates and C<Subscript>org</Subscript> Fluxes in Soledad Lagoon (Cispatá Lagoon System,NW Caribbean Coast of Colombia)

With the aim of evaluating temporal changes in sedimentation and organic carbon (C_org) supplied over the last ~100 years, a sediment core was collected at Soledad Lagoon, a costal ecosystem surrounded by mangroves, located in the Cispatá Estuary (Caribbean coast of Colombia). The core sediments were characterized by low concentrations of calcium carbonate (0.2–2.9%), organic matter (3–8%), total nitrogen (0.11–0.38%), and total phosphorus (0.19–0.65 mg g⁻¹). Fe and Al concentrations ranged from 4% to 5%, and Mn from 356 to 1,047 μg g⁻¹. The ²¹⁰Pb-derived sediment and mass accumulation rates were 1.54 ± 0.18 mm year⁻¹ and 0.08 ± 0.01 g cm⁻² year⁻¹, respectively. The sediment core did not provide evidence of human impact, such as enhancement of primary production or nutrient enrichment, which may result from recent land uses changes or climate change. The C_org fluxes estimated for Soledad Lagoon core lay in the higher side of carbon fluxes to coastal ecosystems (314–409 g m⁻² year⁻¹) and the relatively high C_org preservation observed (~45%) indicate that these lagoon sediments has been a net and efficient sink of C_org during the last century, which corroborate the importance of mangrove areas as important sites for carbon burial and therefore, long-term sequestration of C_org.     

Arsenic removal from aqueous solutions by mixed magnetite–maghemite nanoparticles

In this study, magnetite–maghemite nanoparticles were used to treat arsenic-contaminated water. X-ray photoelectron spectroscopy (XPS) studies showed the presence of arsenic on the surface of magnetite–maghemite nanoparticles. Theoretical multiplet analysis of the magnetite–maghemite mixture (Fe₃O₄-γFe₂O₃) reported 30.8% of maghemite and 69.2% of magnetite. The results show that redox reaction occurred on magnetite–maghemite mixture surface when arsenic was introduced. The study showed that, apart from pH, the removal of arsenic from contaminated water also depends on contact time and initial concentration of arsenic. Equilibrium was achieved in 3 h in the case of 2 mg/L of As(V) and As(III) concentrations at pH 6.5. The results further suggest that arsenic adsorption involved the formation of weak arsenic-iron oxide complexes at the magnetite–maghemite surface. In groundwater, arsenic adsorption capacity of magnetite–maghemite nanoparticles at room temperature, calculated from the Langmuir isotherm, was 80 μmol/g and Gibbs free energy (∆G⁰, kJ/mol) for arsenic removal was −35 kJ/mol, indicating the spontaneous nature of adsorption on magnetite–maghemite nanoparticles.     

Composition and sources of lipid compounds in speleothem calcite from southwestern Oregon and their paleoenvironmental implications

We analyzed speleothem calcite from the Oregon Caves National Monument, southwestern Oregon, to determine the preservation, distribution, concentrations and sources of aliphatic lipid compounds preserved in the calcite. Maximum speleothem growth rate occurs during interglaciations and minimum during glacial intervals. Concentrations of the total lipid compounds range from 0.5 to 12.9 μg g⁻¹. They increase at times of low speleothem growth rate, suggesting dilution, whereas the apparent accumulation rate of lipid compounds tends to be highest during times of fastest speleothem growth rate. Such increased accumulation generally corresponds to times of warm (interglacial) climate, suggesting either a greater source of organic materials during interglacial times and/or greater efficiency of compound capture during more rapid calcite growth. Aliphatic lipid compounds include homologous n-alkanoic acids, n-alkanols and methyl n-alkanoates and sterols with concentrations ranging from 0.3 to 7.8 μg g⁻¹, 0.4 to 1.1 μg g⁻¹, 0.5 to 9.6 μg g⁻¹ and 0.1 to 2.7 μg g⁻¹, respectively. Minor amounts of branched methyl n-alkanoates and dimethyl n-alkanedioates are also present. The high concentrations of methyl n-alkanoates are the result of esterification reactions of free fatty acids in alkaline solutions with high pH values associated with the dripping cave waters. The distribution patterns and geochemical parameters and indices indicate that the major sources of the aliphatic lipids involved leaching from higher plants and microbial residues derived from the soil zone above the cave system. The estimated percentage of microbial inputs ranged from 42 to 90% of the total lipids and also showed an increase in accumulation during warm climates. These well-preserved lipid compounds in speleothem calcite could be used as biomarkers for paleoenvironmental study.     

Weathering fluxes of arsenic from a small catchment in Slovak Republic

Inputs of As to a small catchment due to chemical weathering of bedrock, mechanical weathering of bedrock, and atmospheric precipitation were 71.53, 23.98 and 0.02 g ha⁻¹ year⁻¹, respectively. The output fluxes of As due to mechanical erosion of soil, biological uptake, stream discharge, and groundwater flow were 6.32, 4.77, 0.37 and 0.02 g ha⁻¹ year⁻¹, respectively. The results indicate that arsenic accumulates in soil and regolith with a very high rate. This is attributed to the selective weathering and erosion with respect to arsenic and fixation of arsenic in the secondary solids produced by weathering. The output fluxes of As in stream and groundwater in Vydrica catchment in Slovak Republic (0.39 g ha⁻¹ year⁻¹) based on muscovite–biotite granites and granodiorites were much lower compared to catchments in a gold district in the Czech Republic. These results may be ascribed to the low levels of arsenic pollution measured in Vydrica catchment. The arsenic fluxes were estimated by calculation of mechanical and chemical weathering rates of the bedrocks in Vydrica catchment from mass balance data on sodium and silica. The justification of the steady state of Na and Si is that neither of the elements is appreciably accumulated in plants and in exchangeable pool of ions in soil.     

Source and distribution of trace metals and nutrients in Narmada and Tapti river basins,India

The study was designed to establish the distributions of trace metals, dissolved organic carbon, and inorganic nutrients as well as to assess the extent of anthropogenic inputs into the Narmada and Tapti rivers. Water and sediment qualities are variable in the rivers, and there are major pollution problems at certain locations, mainly associated with urban and industrial centers. The metal concentrations of samples of the aquatic compartments investigated were close to the maximum permissible concentration for the survival of aquatic life, except for higher values of Cu (5–763 μg l⁻¹), Pb (24–376 μg l⁻¹), Zn (24–730 μg l⁻¹), and Cr (70–740 μg l⁻¹) and for drinking water except for elevated concentrations of metals such as Pb, Fe (850–2,060 μg l⁻¹), Cr, and Ni (20–120 μg l⁻¹). In general, the concentrations of trace metals in the rivers vary down stream which may affect the “health” of the aquatic ecosystem and may also affect the health of the rural community that depends on the untreated river water directly for domestic use. The assessment of EF, I _geo, and PLI in the sediments reveals overall moderate pollution in the river basins.     

Pyritization of trace metals in estuarine sediments and the controlling factors: a case in Jiaojiang Estuary of Zhejiang Province,China

Three undisturbed sediment samples were collected from the intertidal zone of the Jiaojiang Estuary of Zhejiang Province, China. The sediments were found to contain remarkably low concentrations of organic carbon (<0.6%) and acid volatile sulfide (AVS) (<30 μmol g⁻¹). The availability of these two substrates likely constrained sulfate reduction and pyritization of several trace metals, respectively. This was especially true at one station where AVS concentrations in the upper 20 cm averaged less than 0.05 μmol g⁻¹. Although the depth dependence of the degree of trace metal pyritization was generally consistent with expectations based on redox conditions, depth profiles of reactive-metal and pyrite-metal concentrations in several cases revealed more complex behavior and a positive correlation between reactive-metal concentrations and pore water metal concentrations.     

Increased As load to the Uchen stream due to mine drainage and soils in the abandoned Kangwon mining district of Korea

To determine the appropriate allocation of resources for the future restoration of the abandoned mining district of Kangwon in Korea, identification of the main pollutants and the main sources discharging these pollutants is crucial. Therefore, a 2-year study was undertaken to quantify the amount of pollutants in the Uchen stream (a potential sink for contamination), which runs through the district, and to determine the potential sources of these pollutants, including mine drainage and soil. Arsenic (As) was the main pollutant in mine drainage and soils showing concentrations above the Korean regulated standard levels of 50 μg L⁻¹ and 50 mg kg⁻¹ for water and soil, respectively. In addition, the pollution index (PI) showed that mine drainages were polluted by As to a moderate (2 ≤ PI < 3) or strong (4 ≤ PI < 5) degree. Consequently, As load in mine drainage and soil contributed to increased amounts of As in the stream. The As loads in mine drainages (11 and 587 g month⁻¹ for mine adit 1 and 2, respectively) accounted for only 9% of the total As load to the stream (6,378 g month⁻¹); and the influence of mine drainages on As contents in the stream was more reliant on the total volume of mine drainage generated rather than the As concentration in the mine drainage. Approximately 91% of the As in the stream was derived from the soils within the study area.     

Arsenic Geochemistry of the Great Dismal Swamp,Virginia, USA: Possible Organic Matter Controls

Surface water samples for arsenic (As) concentration and speciation analysis were collected from organic matter-rich blackwaters of the Lake Drummond portion of the Great Dismal Swamp in southeastern Virginia, USA. Arsenic concentrations and speciation were determined by selective hydride generation, gas chromatography with photoionization detection. Surface waters from the Great Dismal Swamp are high in dissolved organic carbon (DOC) concentrations (445–9,600 μmol/kg) and of low pH (4.2–6.4). Total dissolved As concentrations [i.e., As(III) + As(V)], hereafter As_T, range from 2.2 nmol/kg to 21.4 nmol/kg. Arsenite, As(III), concentrations range from ∼1 nmol/kg to 17.7 nmol/kg, and As(V) ranges from ∼1 nmol/kg to 14.1 nmol/kg. Arsenate, As(V), is the predominant form of dissolved As in the inflow waters to the Great Dismal Swamp, whereas within the swamp proper arsenite, As(III), dominates. Arsenite accounts for 8–37% of As_T in inflow waters west of the Suffolk Scarp, and between 54% and 81% of As_T in Lake Drummond and Great Dismal Swamp waters east of the scarp. Arsenite is strongly correlated to DOC (r = 0.94) and inversely related to pH (r = −0.9), both at greater than the 99% confidence level. Arsenate is weakly related to pH and DOC (r = 0.4 and −0.37, respectively), and neither relationship is statistically significant. No statistical relationships exist between As(V) or As(III) and PO₄ concentrations. The predominance of As(III) and its strong correlation with DOC in Great Dismal Swamp waters suggest that DOC may inhibit As(III) adsorption or form stable aqueous complexes with As(III) in these waters. Alternatively, phytoplankton and/or bacterially mediated reduction of As(V) may be important processes in the organic-rich blackwaters and/or sediment porewaters of the swamp, leading to the prevalence of As(III) in the water column.     

Trace Metals (Cd,Cu, Hg,and Pb) Accumulation Recorded in the Intertidal Mudflat Sediments of Three Coastal Lagoons in the Gulf of California,Mexico

²¹⁰Pb geochronologies of Cd, Cu, Hg, and Pb fluxes were obtained from the intertidal mudflat sediments of the coastal lagoons Chiricahueto, Estero de Urías, and Ohuira in the Mexican Pacific. The Cu and Hg sediment concentrations at the three lagoons fell within the ranges of 6–76 μg g⁻¹ and 0.1 to 592 ng g⁻¹, respectively; Chiricahueto and Estero de Urías sediments had comparable Cd and Pb concentrations within the ranges of 0.2–2.1 μg g⁻¹ and 10–67 μg g⁻¹, respectively; whereas in Ohuira lagoon, Cd concentrations were lower (0.1–0.5 μg g⁻¹) and Pb concentrations were higher (115–180 μg g⁻¹) than in the other lagoons. The metal fluxes (μg cm⁻² y⁻¹) for the three lagoons fell within the ranges of 0.02–0.15 for Cd, 0.7–6.0 for Cu, 0.001–0.045 for Hg, and 0.7–20 for Pb. The Hg pollution in Estero de Urías was attributed to the exhausts of the thermoelectric plant of Mazatlan and the metal enrichment in Chiricahueto and Ohuira was related to the agrochemical wastes from the croplands surrounding these lagoons.     

Geochemical study of arsenic and other trace elements in groundwater and sediments of the Old Brahmaputra River Plain,Bangladesh

The geochemical study of groundwaters and core sediments from the Old Brahmaputra plain of Bangladesh was conducted to investigate the distribution of arsenic and related trace elements. Groundwaters from tube wells are characterized by pH of 6.4–7.4, dissolved oxygen (DO) of 0.8–1.8 mg/l, Ca contents of 5–50 mg/l, and Fe contents of 0.2–12.9 mg/l. Arsenic concentrations ranged from 8 to 251 μg/l, with an average value of 63 μg/l. A strong positive correlation exists between As and Fe (r ² = 0.802; p = 0.001) concentrations in groundwater. The stratigraphic sequences in the cores consist of yellowish silty clays at top, passing downward into grayish to yellowish clays and sands. The uppermost 3 m and lower parts (from 13 to 31 m) of the core sediments are oxidized (average oxidation reduction potential (ORP) +170 and +220 mV, respectively), and the ORP values gradually become negative from 3 to 13 m depths (−35 to −180 mV), indicating that anoxic conditions prevail in the shallow aquifers of the Brahmaputra plain. Age determinations suggest that clay horizons at ~10 m depth were deposited at around 2,000 and 5,000 years BP (¹⁴C ages) during the transgressive phase of sea-level change. Elevated concentrations of As, Pb, Zn, Cu, Ni, Cr, and V are present in the silts and clays, probably due to adsorption onto clay particles. Significant concentrations of As occur in black peat and peaty sediments at depths between 9 and 13 m. A strong positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed onto Fe oxides in aquifer sediments.     

Trends in phosphatase activity along a successional gradient of tidal freshwater marshes on the Cooper River South Carolina

Phosphatase activity was measured in sediments from tidal freshwater habitats adjacent to the Cooper River in South Carolina representing different stages of ecological succession. It was found that sediment (0–5 cm) acid phosphatase activity, alkaline phosphatase activity and phosphodiesterase activity increased with increasing successional stage and phytomass. Acid phosphatase activity in creased from 7.5±1.2 (±1 SD) in subtidal sediment from a shallow open water habitat without vegetation to 61.2±4.9 μmol g⁻¹ hr⁻¹ (μmol of p-nitrophenol released per gram of dry sediment per hour) in intertidal sediments colonized by emergent macrophytes, while alkaline phosphatase activity increased from 2.1±0.1 to 19.01±1.5 μmol g⁻¹ hr⁻¹. Phosphodiesterase activity increased from 1.8±0.1 to 20.2±2.0 μmol g⁻¹ hr⁻¹ along the same gradient. Acid phosphatase activity was highly correlated (R²=0.92, P<0.001) with the organic matter content of the sediment. A study of phosphatase kinetics showed that V_max of all phosphatases also increased along the successional gradient. Trends in phosphatase activity and V_max correlated positively with plant biomass and negatively with concentrations of soluble reactive phosphorus in porewater, sediment extractable phosphorus, and total phosphourus. The porewater N∶P atom ratio decreased along the succession gradient from 25.3 in an early stage, open water community to 13.0 in a community dominated by emergent vegetation. The data also show that the distribution of the forms of phosphorus changed with successional stage. The change in distribution and the increased biological demand for phosphorus that paralleled succession were mediated by the activity of phosphatase enzymes.     

Seasonal variations of phosphorus species in sediment from the middle Adriatic Sea

Phosphorus (P) species concentrations in 0–2 cm surface sediment layer were investigated monthly from November 2001 to December 2002 at the bay, channel and open sea stations in the middle Adriatic. Modified SEDEX method was used for inorganic phosphorus species determination [P in biogenic (P-FD), authigenic (P-AUT), detrital apatite (P-DET) and P adsorbed on to iron oxides and hydroxides (P–Fe)], and organic phosphorus (P-ORG). P-FD, P-AUT and P-DET concentration ranges (1.5–5.4, 0–2.7 and 0.4–3.4 μmol g⁻¹, respectively) were similar at all stations, and showed no obvious common trend of seasonal changes. P–Fe ranged from 1.9 to 11.9 μmol g⁻¹ with the highest values at bay station and higher seasonal oscillations than other inorganic P forms. P-ORG ranged from 0.3 to 18.7 μmol g⁻¹ with higher concentrations at stations of fine-sized sediments and showed increased concentrations in warm part of the year at all stations. Correlation between concentrations of P–Fe in the surface sediment layer and orthophosphate sediment-water interface concentration gradients at bay and channel stations indicated to P–Fe importance in the orthophosphate benthic flux. For the bay station, linkage between sediment P-ORG and chlorophyll a concentrations, primary production and microzooplankton abundance was established, indicating a 1 month delay of sediment response to production fluctuations in the water column.     

Seasonal cycling of arsenic species in a stratified,microtidal estuary (Huon River,Tasmania)

A detailed study of arsenic cycling in the Huon estuary, south-east Tasmania, was undertaken October 1996–September 1998. Arsenic species data were obtained during eight 3-monthly spatial surveys, and a time-series study at a single site in the estuary over a 7-mo period. The data have been correlated with other chemical measurements, including nutrients, salinity, and dissolved oxygen, and also with biological information about the microalgal species present. In the Huon estuary, arsenic cycling is almost entirely biologically influenced. The seasonal cycle of reduced, methylated, and hydride refractory arsenic species was similar to that found in other temperate estuaries of the Northern hemisphere, with greatest production occurring during summer months. Inorganic arsenic concentrations in the Huon River were very low [As(V+III): 0.023–0.057 μg l⁻¹], even when compared with other pristine systems. Concentrations at the seaward end of the estuary were typical of those found in unpolluted coastal seawater. The behavior of As(V+III) in the estuary was nearly conservative in all surveys except those conducted during summer (February), when significant depletion was observed at higher salinity. During these surveys, up to 60% of inorganic arsenic was apparently depleted from the water column with only a small proportion (20–25%) recycled as methylated and UV-labile arsenic species. This was particularly the case in a high salinity side-arm of the estuary, Port Cygnet. The extent of inorganic arsenic depletion correlated with cell numbers of the phytoplanktonPseudo-nitzschia. The fate of the missing inorganic arsenic is unclear, but the co-existence ofPseudo-nitzschia blooms with commercial mussel leases in Port Cygnet could provide one explanation for the loss.