Transport and deposition of organochlorine pesticides from farmland to estuary under tropical regime and their potential risk to aquatic biota.

In this study, residues of organochlorine pesticides (OCPs) in water, suspended particulate matter (SPM), sediment and oysters from the Chanthaburi estuary were monitored closely in the wet and dry seasons for determining potential environmental risks. In water samples, out of twenty OCPs measured, endosulfan and hexachlorocyclohexanes (HCHs) were the two predominant compounds ranging and concentrations between 0.6-13 ng/L and 1-12 ng/L, respectively. Both compounds were found in higher concentrations during the wet season. The two insecticides were significantly correlated with total organic carbon (TOC) in the water with r values of 0.571 (P < 0.05) and 0.440 (P < 0.1), for endosulfan and HCHs respectively suggesting that these chemicals are strongly bound and concentrated by water-soluble organic carbon. As expected, high concentrations of endosulfan and HCHs were associated with SPM and in the surface sediment (0-5 cm) with a concentration ranging from 25-1,219 microg/kg dry wt and 19-110 microg/kg dry wt for SPM, 4-70 microg/kg dry wt and 0.5-50 microg/kg dry wt for surface sediment, respectively. Sediment quality of the Chanthaburi estuary was also assessed in terms of risk to aquatic biota using concentration found in the sediment compared to published allowable threshold levels (U.S. EPA and New York guidelines). Results suggested that most of endosulfan and HCHs levels in sediment samples exceeded the threshold values. Thus potential and environmental risks may be anticipated from levels found in sediment. Oyster from selected farms cultured at the study area appeared to take up both endosulfan and HCHs in proportion to level presented in the water and SPM. The range of endosulfan and HCHs observed in oyster tissue were from 4-46 microg/kg wet wt, and from non-detectable to 8 microg/kg wet wt. respectively. Human risk from oyster consumption was considered by comparing the value measured with allowable threshold level of concerned chemical. The levels of endofulfan and HCHs measured in oyster showed that oysters from this estuary area were safe for consumption.

Export of dissolved organic carbon from a ponded freshwater marsh receiving diverted Mississippi River water.

A series of diversion projects has been implemented to reintroduce Mississippi River water into Louisiana's coastal wetlands in order to reduce wetland loss. The export of dissolved organic carbon (DOC) was measured in a 3,700-ha ponded freshwater marsh that receives diverted Mississippi River water. Results show that highly organic marsh soil and plant material are a source of DOC. DOC, on average, was 3 mg/l greater in outlet water as compared to the concentration in river water entering the wetland. DOC in water leaving the marsh was higher in summer months, with a concentration up to 18 mg/l. Based on a discharge of 1,000 ft3/sec (28.3 m3/sec), it was estimated that the equivalent of 7,335 kg/day of DOC would be exported from the marsh into Lake Cataouatche, located in the northern portion of the Louisiana Barataria Basin estuary. Results suggest that river diversion would likely increase the export of DOC from the marsh as compared to normal transport associated with rainfall and tidal exchange.

Metal concentrations and trace metal Al and Fe ratios in soil of the Chenier Plain, southwest Louisiana coastal zone.

Soil baseline metal concentrations were determined in 220 surface soil samples collected from the Chenier Plain area of southwest coastal Louisiana. Regression relationships between Al, Fe, and various metals were calculated from the data set. The use of these relationships to identify enhanced metal contents in the Chenier Plain soils is presented. Statistical analyses showed an average Al concentration of 1.6% with a maximum concentration of 4.8% and a minimum concentration of 1.3 mg kg(-1). Al concentration in the sediments was positively correlated at the 1% significance level to Cu (r = 0.577**), Pb (r = 0.936**), Cr (r = 0.969**), Ni (r = 0.830**), Cd (r = 0.617**), and Zn (r = 0.506**), but only a 5% significance correlation was found with Mn (r = 0.148*). Average Fe concentration was 1.2% with a maximum value of 3.4% and a minimum concentration of 9.3 mg kg(-1). Fe concentration in the sediments was positively correlated at the 1% significance level to Cu (r = 0.586**), Pb (r = 0.847**), Cr (r = 0.875**), Ni (r = 0.932**), Cd (r = 0.803**), Zn (r = 0.551**), and Mn (r = 0.479**). These relationships were used to evaluate sites for metal contamination. Data from two known contaminated sites, Capitol Lake (Baton Rouge, LA) and Bayou Trepagnier (LA), fell well outside the prediction limits developed with the Chenier Plain Al and Fe metal regression lines for Cr and Zn. Pb and Cd at Capitol Lake were also elevated beyond the metal/Al prediction developed for the Chenier Plain, but the prediction was not out of range when using the metal/Fe regression. Samples from additional sites with no known metal contamination fell within the predictive limits of the regression equations except for Cd and Pb at some sites. Data presented showed that metal/Al and metal/Fe regression relationships can be used as a tool for identifying areas of potential metal contamination in the coastal zone, but must be regionally correlated.

Assessment of Hg contamination and exposure to miners and schoolchildren at a small-scale gold mining and recovery operation in Thailand.

Gold extracted by Hg-amalgamation process, which can cause both health and environmental problems, is widespread in South East Asia including Myanmar, Laos, Cambodia, and Thailand. Small-scale gold mining operations have been carried out since the year 2000 in Phanom Pha District, Phichit Province, Thailand. Since no data is available for evaluating Hg exposure, an investigation of mercury (Hg) contamination and exposure assessment was carried out at this mine site. Environmental monitoring illustrated the total Hg in water was as high as 4 microg/l while Hg in sediment ranged between 102 to 325 microg/kg dry weight. Both Hg deposition from the air (1.28 microg/100 cm(2)/day) and concentration in surface soil (20,960 microg/kg dry weight) were elevated in the area of amalgamation. The potential of Hg exposure to miners as well as to schoolchildren was assessed. The concentrations of Hg in urine of 79 miners who were directly (group I) or indirectly (group II) involved in the gold recovery operation were 32.02 and 20.04 microg/g creatinine, respectively, which did not exceed regulatory limits (35 microg/g creatinine). Hair Hg levels in both groups (group I and group II) also were not significantly higher than the non-exposed group. In terms of risk factors, gender and nature of food preparation and consumption were the two significant variables influencing the concentration of Hg in urine of miners (P < 0.05). A hazard quotient (HQ) was estimated based on the inorganic Hg exposure of individual miners. The HQ values of group I were in a range 16 to 218 times higher than the safety level set as 1. By comparison the group II HQ index was very low (0.03-0.39). The miners in group I who worked and ate food from this area experienced potentially high exposure to Hg associated with the mining process. In a second Hg exposure assessment, a group of 59 schoolchildren who attended an elementary school near the gold mine site was evaluated for Hg exposure. A slightly higher Hg urine concentration was detected in group I and group II (involved and not involved in gold recovery) at average levels of 15.82 and 9.95 microg/g creatinine, respectively. The average Hg values for both groups were below the established levels indicating no risk from Hg intake. Average Hg hair level in all schoolchildren (0.93 microg/g) was not significantly higher than reference group. There were two variables (gender and personal hygiene) which affected the concentration of Hg in urine of schoolchildren (P < 0.05). The result (HQ) also suggested that schoolchildren were not at risk (< 1). Schoolchildren involved in gold mining activities showed some indirect exposure to Hg from the adults working in mining area.

Mercury emission and distribution: Potential environmental risks at a small-scale gold mining operation, Phichit Province, Thailand.

Mercury (Hg) contamination was assessed in environment near an amalgamation gold recovery operation located at a small scale mining operation (Phanom Pha) in Phichit Province, Thailand. Total mercury (THg) concentrations was determined in water, sediment, bivalves in the aquatic environment and as dry deposition or atmospheric fallout on surface soil and leaves of Neem tree (Azadirachta indica Juss. var. siamensis Valeton) near the mining operation. THg in surface soil, Neem flowers (edible part) and rice grain in surrounding terrestrial habitat and with distance from the mining area were also evaluated for possible contamination. Potential environmental risks were evaluated using the hazard quotient equation. Hg analyses conducted in the aquatic habitat showed that THg in water, sediment and bivalves (Scabies cripata Gould) ranged from 0.4 to 4 microg L(-1), 96 to 402 microg kg(-1)dry weight (dw) and 15 to 584 microg kg(-1) wet weight (ww), respectively. High concentrations of THg in water, sediment and bivalves were observed in the receiving stream near the mining operation which was located near the Khao Chet Luk Reservoir. Whereas the THg concentration in water, sediment and bivalves from monitoring stations outside the gold mining operation (upstream and downstream), were considerably lower with the values of 0.4-0.8 microg L(-1), 96-140 microg kg(-1) dw and 88-658 microg kg(-1) dw, respectively. The elevated concentration of Hg found in the sediment near the mining operation was consistent with Hg accumulation measured in bivalves. The elevated Hg levels found in living bivalves collected from highly contaminated sites suggested that the sediment bound Hg was bioavailable. THg in surface soils, brown rice grain (Jasmine rice #105) and Neem flowers of terrestrial habitats were in the range of 16 to 180 microg kg(-1) dw, 190 to 300 microg kg(-1) dw, and 622 to 2150 microg kg(-1) dw, respectively. Elevated concentrations of mercury were found in Neem flowers with the concentration greater than 600 microg kg(-1) ww, which exceeds the maximum permissible concentration reported for biota tissue (500 microg kg(-1) ww). An evaluation of air and soil pollution near the mining operations showed high concentrations of THg in dry deposit from atmospheric fallout (139 microg m(-2) d(-1)), and in surface soil (10,564 microg kg(-1) dw) at station near where open burning of gold ore extracts using the amalgamation process occurred. High or elevated concentration of THg (1172-1301 microg kg(-1) dw) in leaves of Neem tree was also measured near the mining operations. A survey of Hg in surface soil showed elevated Hg concentrations near the site which corresponded to the elevated THg concentration in dry deposition. These results suggested that atmospheric fallout is a major source of Hg to the area surrounding the mining or gold ore extraction. Results also suggest that Hg emitted into the air (estimated to be 60-150 g d(-1)) from the gold mining activities (over the past 10 years) contaminated air, the aquatic environment, surface soil and biota in the area surrounding the gold mining operation.

Partitioning and removal of Cd and Mn using a simulated mangrove wastewater treatment system.

A greenhouse experiment was conducted to study the partitioning and removal of Cd and Mn from wastewater using constructed mangrove (Kandelia candel) wetland treatment system. Three different strengths of artificial wastewater passed through the system in fixed quantities. Artificial seawater was used as a control. Three different compositions were natural wastewater concentration (C1), medium wastewater concentration (C5) and concentrated wastewater concentrations (C10). C1 had the characteristics and strength similar to natural municipal wastewater while C5 and C10 contained five and ten times of the nutrients and heavy metals in C1, respectively. Results showed that the major portion of the Cd and Mn entering the simulated wastewater treatment system entered the sediment pool where approximately 88% to 95% of the Cd, and between 63% and 89% of Mn, was retained. The amount of added Cd and Mn in the wastewater found in plants were between 0.16% to 1.1%, and 1.7% to 13.9%, respectively. Within the total plant pool, roots accounted for between 30% and 39% of Cd, and from 0.65% to 7.3% of Mn; leaves contained between 19.9% to 30.5% of Cd, and from 7.8% to 41.0% of Mn; litterfall contained 12.3% to 20.6% of Cd, and from 15.2% to 70.3% of Mn, respectively. The averaged accumulative coefficients concentration in plant tissues/concentration in sediment in plant for Cd and Mn were 1.22 to 2.40 and 0.02 to 0.08, respectively. Assimilated Cd and Mn were stored in non-activity plant zones such as cell wall, supplimentary cells of the lenticel, stone cells, cell gaps in root and stem, etc. Kandelia candel seedlings had a relative high toxicity resistance to the two heavy metals.

Influence of sediment redox conditions on release/solubility of metals and nutrients in a Louisiana Mississippi River deltaic plain freshwater lake.

The influence of sediment redox conditions on solubility of selected metals and nutrients in sediment from a coastal Louisiana freshwater lake (Lake Cataouatche) receiving diverted Mississippi River water was quantified. Sediment redox was cycled step wise in 50 mV increments between oxidized (-200 to +500 mV) and reduced (+500 to -200 mV) conditions. Changes in sediment oxidation/reduction status and pH influenced solubility of both metals and nutrients. When redox potential (Eh) was increased from -200 to +500 mV, sediment pH decreased from 7.1 to 5.7. When the sediment Eh decreased from +500 to -200 mV, pH increased from 5.7 to 7.1. The increase in sediment acidity upon oxidation resulted in the release of the Pb, Ca, Mg, Al, and Zn into solution. The solution concentration of these elements was inversely proportional to Eh (P

Relationship of sediment redox conditions to methyl mercury in surface sediment of Louisiana Lakes.

Surface sediment from three Louisiana Lakes containing overlying water layer spiked with 2 microg/g (2 ppm) mercury were incubated under oxygenated (air) and nonoxygenated (N2) conditions for determining the impact of oxygen status of overlying water on methylation of Hg in surface sediment from these lakes. The added mercury resulted in a greater than ten fold increase in methyl mercury (MeHg) as compared to native concentration of MeHg. The increase in methyl Hg production was less in sediment in which overlying water was exposed to oxygen rather than nitrogen. Results suggest that methyl Hg production would be less in lakes containing an oxygenated water column. In parallel microcosm studies without added mercury. MeHg decreased in sediment when redox potential of sediment suspension was increased from -200mV to +50mV. Results of these studies demonstrate the importance of oxygenation or redox condition of surface sediment on mercury methylation and demethylation. Sediment conditions, which either reduce methylation or enhance demethylation in surface sediment, will limit the bioavailability of MeHg to the aquatic environment.

Phosphogypsum chemistry under highly anoxic conditions.

Phosphogypsum (PG), primary byproduct from phosphoric acid production, is accumulated in large stockpiles and occupies vast areas of land. Contaminants emanating from PG stacks can impact the environment including waterbodies. The major constraint for PG use in the environment is the presence of metals in high concentrations. Reduction of sulfate found in PG and significance of sulfide production in reducing aqueous concentrations of toxic metals were studied. Mississippi River alluvial sediment amended with PG was equilibrated under controlled redox (-250 mV) and pH (5.5, 6.5, and 7.5) conditions. Phosphogypsum addition resulted in a large increase in sulfide levels in sediment suspensions. As a result, the solubility of spiked heavy metals (Cd and Cr, 100 and 1000 mg kg(-1)) and natural trace elements (As, Ba, and Cd) was significantly reduced by precipitation as insoluble sulfides. Sediment pH also influenced sulfate reduction and sulfide formation in both PG-amended and control sediment. Low sediment pH (5.5) resulted in the highest release of all studied metals and sulfate into sediment solution. This study indicates that if PG or PG-products are placed in neutral to alkaline sediments/soils and/or reducing environments, metals released at toxic levels should be of little concern to the wetland environment.

Environmental conditions associating microcystins production to Microcystis aeruginosa in a reservoir of Thailand.

Three heptapeptide toxins, microcystin-RR, microcystin-RY and microcystin-LR, which can cause health problems in animals and humans were monitored in Bang Phra Reservoir, Thailand using reversed-phase high performance liquid chromatography. The concentrations of the three toxins in the reservoir varied greatly depending on location and time water samples were collected. Water quality parameters such as light intensity, temperature, pH, dissolved oxygen, suspended solid, chemical oxygen demand, dissolved organic carbon, total nitrogen, total phosphorus, ammonia, nitrate, phosphate, total dissolved nitrogen, total dissolved phosphorus and chlorophyll-a were also measured in parallel with microcystin determinations. Relationships among water quality parameters, toxins and chlorophyll-a were established. Toxin concentration increased in proportion to increases in total phosphorus, fraction of dissolved phosphorus, but was inversely correlated with water pH and total suspended solids. The other measured parameters in the study showed no correlations to toxin level in reservoir water. Significant correlations between chlorophyll-a and suspended solids, phosphate, nitrate and ammonia were observed suggesting that nitrogen and phosphorus are the two major nutrients governing growth of algae in the reservoir. This relationship suggests that algal production as well as toxin concentration are dependant on nutrient levels in the water body, since both measured light intensity and temperature level was favorable for algal growth. A small algal bloom observed in the rainy season of each year (lasting for only a couple of months) paralleled measured increases in toxin concentration, chlorophyll-a, TP and TN in the water column. Toxin level in the water column remain detectable for 3-4 months period following the initiation of algal bloom. Results indicate that major blooms are likely to occur following the raining season which usually occurs near the end of October when runoff would increase nutrient level entering the reservoir. This study also demonstrated that an ongoing field-monitoring program is needed in these lakes and reservoirs for predicting toxic level of microcystin production for use in risk assessment and for alerting the public to potential health hazards. Concentration of toxin in the reservoir can perhaps be controlled by reducing non point source nutrient input within the watershed.

Adsorption and desorption of mercury by Bangpakong River sediments as influenced by salinities.

Mercury adsorption and desorption by Bangpakong River sediments (pH range 6.8-7.8) of Thailand were investigated at salinity levels of 0, 5, 15 and 30@1000 using a batch equilibration techniques. Using Freundlich isotherm adsorption and desorption data collected represented a nonlinear form. A significant portion (90-99%) of added Hg (2-10 mg L-1) was sorbed by the sediment. Mercury adsorption isotherms or percentage adsorbed were similar among the four salinities tested. In the absence of salinity, Hg adsorption was highly influenced by pH. Whereas in the presence of salinity gradients, Hg(II)-organic complexes predominated over Hg(II)-Cl complexes, neutralizing effect of chloride concentrations and pH on the adsorption phenomena. Organic matter and clay contents of sediment were responsible for the Hg adsorption. Fe and Mn oxides showed negative correlation with the Hg adsorption capacity (r = -0.549 and -0.594 respectively). Increase in Hg desorbed from the sediments occurred only at the 30@1000 salinity level. The Hg adsorption-desorption characteristics of the sediments studied exhibited a very strong irreversible sorption of added inorganic Hg. River sediment such as sediment as shown in this study with significant levels of organic matter and clay have the potential to retain Hg making it less bioavailable and mobile thus reducing potential toxicity to aquatic organisms in the environment.

Mercury distribution in sediment profiles of six Louisiana Lakes.

A study was conducted of six Louisiana Lakes to examine the relationship between sediment properties including mercury content and health advisories associated with mercury levels in fish. Comparison was made between three lakes with health advisories (Black Lake, Chicot Lake, and Henderson Lake) and three lakes where the levels of mercury in fish are below health advisory levels (False River, Lake St. John, and Miller Lake). Three sediment core samples were collected from each lake and sectioned into 2-cm increments to a depth of 20 cm. Sediment properties measured in each depth increment of the sediment profile included total mercury, 137Cs activity (for sedimentation rate), and sediment organic matter content. Of the lakes studied, those lakes that have health advisories for mercury tended to have higher total mercury contents, usually higher sediment organic matter contents, and higher sedimentation rates than sediments in lakes where health advisories for mercury are not issued.

The effects of crude oil and the effectiveness of cleaner application following oiling on US Gulf of Mexico coastal marsh plants.

Field studies were conducted in two different marsh habitats in Louisiana coastal wetlands to evaluate the effects of oiling (using South Louisiana Crude oil, SLC) and the effectiveness of a shoreline cleaner (COREXIT 9580) in removing oil from plant canopies. The study sites represented two major marsh habitats; the brackish marsh site was covered by Spartina patens and the freshwater marsh was covered by Sagittaria lancifolia. Field studies were conducted in each habitat using replicated 5.8 m2 plots that were subjected to three treatments; oiled only, oiled + cleaner (cleaner was used 2 days after oiling), and a control. Plant gas exchange responses, survival, growth, and biomass accumulation were measured. Results indicated that oiling led to rapid reductions in leaf gas exchange rates in both species. However, both species in 'oiled + cleaned' plots displayed improved leaf conductance and CO2 fixation rates. Twelve weeks after treatment initiation, photosynthetic carbon fixation in both species had recovered to normal levels. Over the short-term, S. patens showed more sensitivity to oiling with SLC than S. lancifolia as was evident from the data of the number of live shoots and above-ground biomass. Above-ground biomass remained significantly lower than control in S. patens under 'oiled' and 'oiled + cleaned' treatments while it was comparable to controls in S. lancifolia. These studies indicated that the cleaner removed oil from marsh grasses and alleviated the short-term impact of oil on gas exchange function of the study plants. However, use of cleaner had no detectable effects on above-ground biomass production or regeneration at the end of the first growing season in S. patens. Similarly, no beneficial effects of cleaner on carbon fixation and number of live shoots were apparent beyond 12 weeks in S. lancifolia.

Impact of redox conditions on metolachlor and metribuzin degradation in Mississippi flood plain soils.

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd(-1) and 25 ngd(-1), respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd(-1) and 32.5 ngd(-1), respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd(-1) and 12.0 ngd(-1) for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd(-1) and 5.35 ngd(-1). Metribuzin degraded faster (12.0 ngd(-1)) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd(-1)).