Pollution by hexachlorobenzene and pentachlorophenol in the coastal plain of São Paulo state, Brazil

Organochlorine compounds were dumped by chemical industries during the 1970s in many areas of the coastal plain of São Paulo state in Brazil. These dumps, located on hillsides and in valleys, in both rural and urban environments, are responsible for soil and water pollution. The objective of this work was to determine how the pollutants have spread in an area occupied by a spodosol-type soil mantle. The study combines soil morphological observations with soil and water analysis of hexachlorobenzene (HCB) and pentachlorophenol (PCP) in soil toposequences. The results indicate that the highest pollutant concentrations are observed near the dump site and that the compounds contamination is increasing. A map integrating topography and chemical concentrations was created to visualize the spatial distribution of HCB levels in the landscape. Physical and chemical analyses were performed to measure HCB and PCP levels in the soil. Soil water appears to act as a vector of HCB, probably through complexation with and dispersal of dissolved organic matter. The persistence of HCB at the studied site is most likely due to the low pH values in combination with a high content of organic matter. HCB was consistently found in higher concentrations than PCP. It is plausible that the cause of this difference is that PCP is degraded more easily under sunlight than HCB and that degradation of PCP under acid conditions leads to the formation of HCB. © 2003 Published by Elsevier B.V.

Seasonal behavior of mercury species in waters and sediments from the Negro River Basin, Amazon, Brazil

Total (HgT), reactive (HgR) and organic (Hg ORG) mercury species have been quantified in non-filtered waters collected from the Negro River Basin, Amazon (from January/2002 through January/2004), in both black and white water bodies. Black waters presented the highest HgT, HgORG and HgR concentration (29.1 ng L-1, 1.63 ng L-1 and 3.9 ng L-1, respectively), while, white waters presented the lowest HgT, Hg ORG and HgR concentration (8.8 ng L-1, 0.49 ng L-1 and 1.2 ng L-1, respectively). An inverse correlation between HgT and the water level over the basin was obtained, although the HgORG concentration has increased in the first rainy months and then decreased as the water level rose. Total mercury in surface sediments (0-10 cm) ranged from 70 to 271 mg kg-1 being the methylmercury 0.47-1.79 % of this stock. The results indicate that HgR and the labile dissolved organic matter were introduced into the aquatic environment during the flooding season, especially in the earlier stages, thus contributing to mercury methylation. ©2007 Sociedade Brasileira de Química.

Bio-Optical Properties of the Inner Continental Shelf off Santos Estuarine System, Southeastern Brazil, and their Implications for Ocean Color Algorithm Performance

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cylindrospermopsis raciborskii exudate-Cu complexes: impact on copper dynamics and bioavailability in an aquatic food chain

The increasing contamination of aquatic environments motivates studies on the interactions among natural dissolved organic matter, metals, and the biota. This investigation focused on the organic exudates of the toxic cyanobacteria Cylindrospermopsis raciborskii as a Cu carrier through a three-level aquatic trophic chain (bacteria, protozoa, and copepod). The effects of bacteria activity and growth on the metal-organic complexes were evaluated through changes in free Cu2+ ions, total dissolved, and total particulate Cu. To be sure that the added copper would be complexed to the exudates, its complexing properties were previously determined. The cyanobacteria exudate-Cu complexes were furnished to bacteria that were further used as a food source to the protozoan Paramercium caudatum. This was then furnished as food to the copepod Mesocyclops sp. The results showed that, in general, the cyanobacterial exudates decreased Cu bioavailability and toxicity to the first trophic level (bacteria), but because the heterotrophic bacteria accumulated Cu, they were responsible for the transference for the otherwise low availability metal form. Both the bacteria and protozoan organisms accumulated Cu, but no metal accumulation was detected in the copepods.

Factors controlling water-column respiration in rivers of the central and southwestern Amazon Basin

We examined the factors controlling the variability in water-column respiration rates in Amazonian rivers. Our objectives were to determine the relationship between respiration rates and the in situ concentrations of the size classes of organic carbon (OC), and the biological source (C-3 and C-4 plants and phytoplankton) of organic matter (OM) supporting respiration. Respiration was measured along with OC size fractions and dissolved oxygen isotopes (delta O-18-O-2) in rivers of the central and southwestern Amazon Basin. Rates ranged from 0.034 mu mol O-2 L-1 h(-1) to 1.78 mu mol O-2 L-1 h(-1), and were four-fold higher in rivers with evidence of photosynthetic production (demonstrated by delta O-18-O-2<24.2 parts per thousand) as compared to rivers lacking such evidence (delta O-18-O-2>24.2 parts per thousand; 1.35 +/- 0.22 vs. 0.30 +/- 0.29 mu mol L-1 h(-1)). Rates were likely elevated in the former rivers, which were all sampled during low water, due to the stimulation of heterotrophic respiration via the supply of a labile, algal-derived substrate and/or the occurrence of autotrophic respiration. The organic composition of fine particulate OM (FPOM) of these rivers is consistent with a phytoplankton origin. Multiple linear regression analysis indicates that [FPOC], C:N-FPOC ratios, and [O-2] account for a high amount of the variability in respiration rates (r(2) = 0.80). Accordingly, FPOC derived from algal sources is associated with elevated respiration rates. The delta C-13 of respiration-derived CO2 indicates that the role of phytoplankton, C-3 plants, and C-4 grasses in supporting respiration is temporally and spatially variable. Future scaling work is needed to evaluate the significance of phytoplankton production to basin-wide carbon cycling.

Short-term response of the Ca cycle of a montane forest in Ecuador to low experimental CaCl 2 additions

The tropical montane forests of the E Andean cordillera in Ecuador receive episodic Sahara-dust inputs particularly increasing Ca deposition. We added CaCl2 to isolate the effect of Ca deposition by Sahara dust to tropical montane forest from the simultaneously occurring pH effect. We examined components of the Ca cycle at four control plots and four plots with added Ca (2 × 5 kg ha–1 Ca annually as CaCl2) in a random arrangement. Between August 2007 and December 2009 (four applications of Ca), we determined Ca concentrations and fluxes in litter leachate, mineral soil solution (0.15 and 0.30 m depths), throughfall, and fine litterfall and Al concentrations and speciation in soil solutions. After 1 y of Ca addition, we assessed fine-root biomass, leaf area, and tree growth. Only < 3% of the applied Ca leached below the acid organic layer (pH 3.5–4.8). The added CaCl2 did not change electrical conductivity in the root zone after 2 y. In the second year of fertilization, Ca retention in the canopy of the Ca treatment tended to decrease relative to the control. After 2 y, 21% of the applied Ca was recycled to soil with throughfall and litterfall. One year after the first Ca addition, fine-root biomass had decreased significantly. Decreasing fine-root biomass might be attributed to a direct or an indirect beneficial effect of Ca on the soil decomposer community. Because of almost complete association of Al with dissolved organic matter and high free Ca2+ : Al3+ activity ratios in solution of all plots, Al toxicity was unlikely. We conclude that the added Ca was retained in the system and had beneficial effects on some plants.

The Value of Adding Optics to Ecosystem Models: A Case Study

Many ecosystem models have been developed to study the ocean's biogeochemical properties, but most of these models use simple formulations to describe light penetration and spectral quality. Here, an optical model is coupled with a previously published ecosystem model that explicitly represents two phytoplankton (picoplankton and diatoms) and two zooplankton functional groups, as well as multiple nutrients and detritus. Surface ocean color fields and subsurface light fields are calculated by coupling the ecosystem model with an optical model that relates biogeochemical standing stocks with inherent optical properties (absorption, scattering); this provides input to a commercially available radiative transfer model (Ecolight). We apply this bio-optical model to the equatorial Pacific upwelling region, and find the model to be capable of reproducing many measured optical properties and key biogeochemical processes in this region. Our model results suggest that non-algal particles largely contribute to the total scattering or attenuation (> 50% at 660 nm) but have a much smaller contribution to particulate absorption (< 20% at 440 nm), while picoplankton dominate the total phytoplankton absorption (> 95% at 440 nm). These results are consistent with the field observations. In order to achieve such good agreement between data and model results, however, key model parameters, for which no field data are available, have to be constrained. Sensitivity analysis of the model results to optical parameters reveals a significant role played by colored dissolved organic matter through its influence on the quantity and quality of the ambient light. Coupling explicit optics to an ecosystem model provides advantages in generating: (1) a more accurate subsurface light-field, which is important for light sensitive biogeochemical processes such as photosynthesis and photo-oxidation, (2) additional constraints on model parameters that help to reduce uncertainties in ecosystem model simulations, and (3) model output which is comparable to basic remotely-sensed properties. In addition, the coupling of biogeochemical models and optics paves the road for future assimilation of ocean color and in-situ measured optical properties into the models.

Abundance of bacteria, cyanobacteria and nanoflagellates at sime series station DYNAPROC

The variability in microbial communities (abundance and biomass), bacterial production and ectoaminopeptidase activity, particulate and dissolved organic carbon (POC, DOC), and particulate and dissolved lipids was examined in spring 1995 in the northwestern Mediterranean, where a transition from the end of a bloom to pre-oligotrophic conditions was observed. Four time series of 36 h each and 4 h sampling intervals were performed at 5 m and at the chlorophyll maximum (30 m) between 11 and 31 May. Simultaneous measurements of pigments, abundance of hetero- and autotrophic flagellates, bacteria and POC enabled the estimation of living POC (defined as autotrophic-C plus heterotrophic-C biomass), and thus the detrital organic carbon. During the first 2 time series (11 to 15 May), the bacterial-C biomass was higher than the autotrophic-C biomass at 5 m (ratio 1.4 and 1.7), whereas the opposite trend was observed in the chlorophyll peak (ratio 0.7 for the first cycle). However, at the end of May, autotrophic-C biomass was equivalent to bacterial-C biomass at both depths studied. The detrital pool remained a more or less constant fraction of the POC (52, 53 and 47% on 11-12 May, 14-15 May and 30-31 May) at the chlorophyll peak, whereas it decreased significantly with time (62 to 53%) at 5 m. Relationships between bacterial activities and evolution of available resources were not systematically evidenced from our 36 h diel cycle data. Nevertheless, at the monthly scale, comparison of bacterial carbon demand (BCD) to potential carbon resources (detrital POC and DOC) showed that bacteria fed differently on the various pools. From ectoaminopeptidase turnover rates and detrital POC, the potential hydrolysis rate of detritus was calculated. Depending on the choice of conversion factors for bacterial production and estimates of hydrolysis turnover rates, it was shown that bacterial hydrolysis of detritus could be one of the DOC accumulation sources. We observed that the percentage of BCD supplied by detrital POC hydrolysis increased in the surface and decreased in the chlorophyll peak. An index of lipid degradation in POC, the lipolysis index, increased during the month at 5 m, also indicating a higher hydrolysis of POC. The opposite trend was observed in the chlorophyll maximum layer. The selective decrease in dissolved lipids in DOC in the chlorophyll maximum layer, particularly free fatty acids, also suggests that bacteria utilized increased fractions of carbon sources from the DOC. We concluded that partitioning between DOC and detritus as resources for bacteria can change during the rapid transition period from mesotrophy to oligotrophy in the northwestern Mediterranean.

Physico-chemical characteristics and ikaite content of brine and ice samples taken during SIPEX and DDU campaigns in East Antarctica, 2007

Calcium carbonate precipitation in sea ice is thought to potentially drive significant CO2 uptake by the ocean. However, little is known about the quantitative spatial and temporal distribution of CaCO3 within sea ice, although it is hypothesized that high quantities of dissolved organic matter and/or phosphate (common in sea ice) may inhibit its formation. In this quantitative study of hydrous calcium carbonate as ikaite, sea ice cores and brine samples were collected from pack and land fast sea ice between September and December 2007 during two expeditions, one in the East Antarctic sector and the other off Terre Adélie. Samples were analysed for CaCO3, salinity, dissolved organic carbon/nitrogen, inorganic phosphate, and total alkalinity. No relationship between these parameters and CaCO3 precipitation was evident. Ikaite was found mostly in the uppermost layers of sea ice with maximum concentrations of up to 126 mg ikaite per litre melted sea ice being measured, although both the temporal and horizontal spatial distributions of ikaite were highly heterogeneous. The precipitate was also found in the snow on top of the sea ice at some of the sampling locations.

(Table 1) Biomass (as energy) of different elements of the planktonic community in the Equatorial Pacific in the 0-150 m layer

An analysis was made of composition and content of nutrients, salts, particulate and dissolved organic matter, and various plankton groups in a series of samples collected by a 140-liter sampling bottle to depth up to 150 m at 4 equatorial stations between 97° and 154°W. Large and small phytoplankton, bacteria (aggregated and dispersed), heterotrophic flagellates, infusorians, radiolarians, foraminifers, fine filter-feeders, small and large, mostly herbivorous copepods, cyclopoids, predatory calanoids, and other predators were investigated separately. Trophic relations between these elements are established from personal and published data, and rate of their metabolism and some other physiological parameters are determined. Such functional characteristics as extent of satisfaction of food requirements of organisms belonging to various trophic groups, intensity of trophic relations, balance between production and consumption by individual elements of the community, ecological efficiency, and net and specific production of the groups distinguished, of individual trophic levels, of total zooplankton, and of the community as a whole are calculated. Variations of these characteristics along the equator with decreasing upwelling intensity are examined and their possible causes and mechanisms are discussed.

Biogeochemical measurements at the Antarctic Peninsula

Size-fractionated chlorophyll a and photosynthetic carbon incorporation, microbial oxygen production and respiration and particulate vertical flux were measured in January 1996 at three regions, characterized by distinct hydrographic fields and planktonic communities, of the Antarctic Peninsula: (1) a diatom-Phaeocystis sp., dominated community associated with the relatively stratified waters of the Gerlache Strait, (2) a nanoplankton-Cryptomonas sp. dominated assemblage at the Gerlache-Bransfield confluence; and (3) a nano- and picoplankton community in mixed waters of the Bransfield Strait. Despite the marked differences in both community structure and total phytoplankton biomass and primary production, and against predictions from models about trophic control of C export, the lowest respiration rates were measured at Bransfield (pico- and nanoplankton), and no difference was observed between the Gerlache (large diatoms) and Bransfield stations in relative vertical particle flux (6.4 vs. 5.1 % of suspended C; 14.9 vs. 10.4 % of net community production, respectively). Growth and loss rates of the phytoplankton population studied for each community indicate that microbial populations can be explained by in situ growth, but spatial (diatom-Phaeocystis sp., bloom) and temporal (diatom-Phaeocystis sp. bloom and nanoplankton communities) scales of study were shown to be insufficient for addressing the coupling between primary production and biogenic carbon export, especially after the appreciation of the accumulation of dissolved organic carbon in the water column. This would explain the unexpected results and highlights the necessity of including the mechanisms controlling accumulation and consumption of dissolved organic matter into conceptual models about the trophic control of C export.