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Piero R Gardinali

Publications and source records attributed to Piero R Gardinali.

11 recordsLinked to original sources

Free radical chemistry of disinfection-byproducts. 1. Kinetics of hydrated electron and hydroxyl radical reactions with halonitromethanes in water.

Halonitromethanes are disinfection-byproducts formed during ozonation and chlorine/chloramine treatment of waters that contain bromide ion and natural organic matter. In this study, the chemical kinetics of the free-radical-induced degradations of a series of halonitromethanes were determined. Absolute rate constants for hydroxyl radical, *OH, and hydrated electron, e(aq)-, reaction with both chlorinated and brominated halonitromethanes were measured using the techniques of electron pulse radiolysis and transient absorption spectroscopy. The bimolecular rate constants obtained, k (M(-1) s(-1)), for e(aq)-/*OH, respectively, were the following: chloronitromethane (3.01 +/- 0.40) x 10(10)/(1.94 +/- 0.32) x 10(8); dichloronitromethane (3.21 +/- 0.17) x 10(10)/(5.12 +/- 0.77) x 10(8); bromonitromethane (3.13 +/- 0.06) x 10(10)/(8.36 +/- 0.57) x 10(7); dibromonitromethane (3.07 +/- 0.40) x 10(10)/(4.75 +/- 0.98) x 10(8); tribromonitromethane (2.29 +/- 0.39) x 10(10)/(3.25 +/- 0.67) x 10(8); bromochloronitromethane (2.93 +/- 0.47) x 10(10)/(4.2 +/- 1.1) x 10(8); bromodichloronitromethane (2.68 +/- 0.13) x 10(10)/(1.02 +/- 0.15) x 10(8); and dibromochloronitromethane (2.95 +/- 0.43) x 10(10) / (1.80 +/- 0.31) x 10(8) at room temperature and pH approximately 7. Comparison data were also obtained for hydroxyl radical reaction with bromoform (1.50 +/- 0.05) x 10(8), bromodichloromethane (7.11 +/- 0.26) x 10(7), and chlorodibromomethane (8.31 +/- 0.25) x 10(7) M(-1) s(-1), respectively. These rate constants are compared to recently obtained data for trichloronitromethane and bromonitromethane, as well as to other established literature data for analogous compounds.

Dimethylnitrosamine↗

Assessing the effects of Irgarol 1051 on marine phytoplankton populations in Key Largo Harbor, Florida.

The antifouling boosting agent Irgarol 1051 is a strong inhibitor of the photosystem II (PSII) with high efficiency/toxicity towards algae. However, because some phytoplankton species are more sensitive to Irgarol than others, its persistent release into the environment could result in adverse changes in the phytoplankton community structure at heavily impacted sites such as marinas. Continuous monitoring in the Florida Keys showed Irgarol concentrations of up to 635 ngL(-1) in the canal system leading to Key Largo Harbor Marina (KLH) with a sharp decrease in concentration at stations offshore from the mouth of the canal. Preliminary phytoplankton community assessments from surface water samples collected in KLH between February and August 2004 showed changes in several phytoplankton species in concordance with the increase of the herbicide concentrations. Typical responses include an increase in the abundance of eukaryotes and Cryptomonas sp. as Irgarol concentrations increase.

Chlorophyll↗

Trace determination of 1-aminopropanone, a potential marker for wastewater contamination by liquid chromatography and atmospheric pressure chemical ionization-mass spectrometry.

1-Aminopropanone (APR) is a volatile aminoketone of human origin that has been identified in raw sewage and surface waters. However, the traditional methodology for the determination of APR is extremely complicated and requires a skilled chemist to achieve consistent results. This investigation presents a novel and simple method for the analysis of APR by direct derivatization in aqueous media. APR is synthesized as its hydrochloride and derivatized using mercaptoethanol and o-phthalaldehyde. The product of reaction is separated on a 15 cm x 4.6 mm Luna C-18 column (1 mL/min, 45:55 acetonitrile: Water) and detected using a single quadrupole mass spectrometer detector operated in atmospheric pressure chemical ionization (APCI) mode. Method detection limits as low as 100 nM were routinely obtained with a precision of 1.7%. Recoveries of APR were always found to be greater then 88% in surface and wastewater samples fortified at three different levels. However, despite the robustness of the method and the fact that APR was consistently detected in urine it was not present in a variety surface or wastewaters analyzed during the course of the study. These results pose a critical question on the use of APR as a tracer for human derived wastewaters.

Acetone↗

Monitoring of Irgarol 1051 concentrations with concurrent phytoplankton evaluations in East Coast areas of the United States.

The objectives of this study were to measure: (1) Irgarol and GS26575 (major metabolite) during the peak 2004 boating season at selected marinas and reference areas in the Carolinian Zoogeographic Province of the Eastern United States; (2) Irgarol and GS26575 at selected stations during the summer months in the Back Creek/Severn River area in Maryland in 2003 and 2004; and (3) structural and functional characteristics of resident phytoplankton communities concurrently with Irgarol and GS26575 monitoring in Back Creek/Severn River area. Irgarol concentrations from 14 marinas in the Carolinian Province ranged from non-detectable (<1 ng/L) to 85 ng/L; concentrations were less than 16 ng/L at all reference sites. The probability of exceeding the plant 10th centile for Irgarol (251 ng/L) was less than 0.6% for all marinas and 0.01% for all reference areas. These data suggest low ecological risk from Irgarol exposure for both marina and reference areas in the Carolinian Province. Irgarol concentrations ranged from 5 ng/L at the Severn River reference site to 1,816 ng/L in Port Annapolis marina during the two year study. Ecological risk from Irgarol exposure was high for the Port Annapolis marina sites based on a probability of exceeding the plant 10th centile. However, risk was low for Severn River and Severn River reference sites. Functional and structural measures of resident phytoplankton communities in the Back Creek and Severn River did not suggest that these target species are impaired in the Port Annapolis marina area where probabilistic analysis predicted adverse effects from Irgarol exposure.

Analysis of Variance↗

Occurrence of Irgarol 1051 and its major metabolite in Maryland waters of Chesapeake Bay.

Irgarol and its major metabolite (GS26575) were measured in Maryland waters of Chesapeake Bay: (1) in and near 10 marinas, a mainstem Bay site and two Severn River locations during a general survey in July and December of 2002; (2) at various sites in the Port Annapolis Marina and the Severn River area during March of 2002 before the boating season began; and (3) during July (peak boating season) in the same Port Annapolis Marina and Severn River sites area during both an ebb and flood tide. Irgarol concentrations ranged from 1.82 ng/l at the mid-Bay site to 585 ng/l in Port Annapolis marina during the July and December general survey. An Irgarol 90th centile of 239 ng/l was reported for the 10 marina sites, two Severn River sites and one mainstem site sampled during the general survey conducted in July and December. Temporal analysis of all pooled data showed that 90th centiles were over seven times higher in July when compared to December. A comparison of Irgarol concentrations at 12 sites in the Port Annapolis marina and Severn River area during both an ebb and flood tide in July showed no consistent trend with tidal cycle by site although significant reductions in concentrations were reported with distance from the three Port Annapolis marina sites. Ecological risk from Irgarol exposure was judged to be low for most Chesapeake Bay sites sampled. Possible exceptions were Port Annapolis marina, Severn River sites in close proximity to this marina and Chesapeake Harbor marina where Irgarol concentrations exceeded a conservative effects threshold during the peak boating season in July. Ecological risk from GS26575 exposure was low for all sites.

Ecosystem↗

Occurrence and transport of Irgarol 1051 and its major metabolite in coastal waters from South Florida.

Irgarol 1051, a boosting antifouling agent often used to supplement copper based paints was found in surface waters from South Florida at stations collected from the Miami River, Biscayne Bay and selected areas of the Florida Keys. Concentrations of the herbicide ranged from below the method detection limit (1 ng/L) to as high as 182 ng/L in a canal system in Key Largo. The herbicide was present at 93% of the stations and often found in conjunction with its descyclopropyl metabolite (M1) previously reported to be the major degradation product of Irgarol under natural environmental conditions. The 90th percentile concentration calculated for all South Florida samples was 57.6 ng/L. Based on available data on the toxicity of Irgarol to algae and coral, only two stations (approximately 3%) ranked above the LC50 of 136 ng/L reported for the marine algae Naviculla pelliculosa and above the 100 ng/L level reported to reversibly inhibit photosynthesis of intact corals. However, a basic dissipation model for Irgarol using the Key Largo Harbor station as a point source indicated that concentrations of the herbicide decreased rapidly and concentrations below the MDL are observed within 2000 m of the source. No major coral based benthic habitats are documented for all the stations surveyed at distances that Irgarol may pose a substantial risk. However, other types of submerged vegetation like seagrasses are common around the marinas and the effects of Irgarol to such endpoints should be investigated further.

Atlantic Ocean↗

Uptake and depuration of toxic halogenated aromatic hydrocarbons by the American oyster (Crassostrea virginica): a field study.

Uptake and depuration of toxic chlorinated compounds such as planar polychlorinated biphenyls (PCBs 77, 126, 169), 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and 2,3,7,8-tetrachlorodibenzofuran (TCDF) were monitored during a 50-day field study where American oysters (Crassostrea virginica) were transplanted back and forth between a heavily polluted area (Houston Ship Channel, SC) and a relatively unimpacted area (Hanna's Reef, HR) within Galveston Bay, TX. In general, low molecular weight, less lipophilic compounds accumulated in the oysters to a larger extent than high molecular weight ones. Estimated half-lives for planar PCB congeners 77 and 126 were 28 and 51 days, respectively for depuration of newly contaminated oysters (HR-SC-HR) while longer half-lives (42 and 60 days, respectively) were observed for the same compounds as they were eliminated from chronically contaminated individuals (SC-HR). Estimated half-lives for 2,3,7,8-TCDD and 2,3,7,8-TCDF were 35 and 36 days, respectively and were similar to the tetrachlorinated biphenyls (PCBs 77 and 81). Compared with ortho-substituted PCB congeners of the same chlorination level, the more toxic PCBs take longer to depurate from the oysters. With few exceptions, elimination of all toxic compounds investigated proceeded at a slower rate from the chronically exposed population that from the newly contaminated one.

Animals↗

Organic compounds and trace metals of anthropogenic origin in sediments from Montego Bay, Jamaica: assessment of sources and distribution pathways.

Surface sediments throughout Montego Bay, Jamaica were collected in 1995 and analyzed for their trace metal and trace organic contaminant content. A variety of trace metals, petroleum hydrocarbons, polycyclic aromatic hydrocarbons, coprostanol as well as chlorinated hydrocarbons such as pesticides and polychlorinated biphenyls were detected and provide evidence for several anthropogenic inputs to the bay. Two main sources of these chemicals are the Montego River and the North Gully, the latter being more significant. Particle-associated pollutants were found to be distributed along the Montego River plume, as well as being transported by the prevailing water currents to the South-Western sections of the bay, probably through re-suspension of enriched fine sediments from the North Gully outfall area.

Environmental Monitoring↗

Occurrence of IRGAROL 1051 in coastal waters from Biscayne Bay, Florida, USA.

Surface water samples from marinas, commercial ports and open bay areas collected from Biscayne Bay and the Miami River, Florida, USA, were analyzed for the occurrence of IRGAROL 1051 by GC/MS. The anifouling boosting herbicide was found in 80% (46/57) of the samples collected between March 1999 and September 2000. Concentrations within the bay range between non-detected (<1 ppt) and 61 ppt (ng/L) and were generally low compared with levels reported in European or Japanese waters. Aside from the elevated concentrations observed along the Miami River South Fork (61 ppt), the highest concentrations observed in the bay corresponded to marinas with high density of pleasure craft and restricted water circulation. In contrast, occurrence of IRGAROL 1051 along the commercial port or the cruise line terminal was generally lower (<1-2.2 ppt). Concentrations around Coconut Grove Marina were consistently higher (5-12 ppt) than the rest of the bay waters during the whole period of time surveyed.

Environmental Monitoring↗

Trace determination of caffeine in surface water samples by liquid chromatography--atmospheric pressure chemical ionization--mass spectrometry (LC-APCI-MS).

A new method based on liquid-liquid extraction (LLE) coupled to reverse phase liquid chromatography and atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) has been applied to determine trace amounts of caffeine (1,3,7-trimethylxanthine) in surface water samples from a near coastal ecosystem such as Biscayne Bay, Florida. The rational behind the development of such method will be to evaluate the use of unmetabolized caffeine as a potential dissolved phase tracer of human waste contamination. The method allows for the determination of caffeine at levels as low as 4.0 ng/l (ppt) in both salt and freshwater by extracting and concentrating a 1-1 water sample to a final volume of 500 microl and using HPLC separation coupled to an atmospheric pressure chemical ionization mass spectrometry (APCI-MS) system operated in selected ion monitoring (SIM) for the protonated molecular ions (M + H(+)). Samples from different portions of Biscayne Bay and the Miami River, one of its major tributaries, were analyzed and caffeine was detected in those areas previously identified for consistently exceeding the water quality criteria for fecal coliform bacteria contamination. The caffeine concentration in the samples with positive detection was generally low at levels equal or lower than 41 ng/l. However, there is a marked difference between samples collected in open bay areas and those collected from the Miami River.

Atmospheric Pressure↗